Mixed catalysts with unbridged hafnocenes with -CH2-SiMe3 moieties

ABSTRACT

The present disclosure provides a supported catalyst system and process for use thereof. In particular, the catalyst system includes an unbridged metallocene compound, an additional unbridged metallocene compound having a structure different than the first unbridged metallocene compound, a support material and an activator. The catalyst system may be used for preparing polyolefins.

PRIORITY CLAIM

This application claims priority to and the benefit of U.S. Ser. No.62/541,372, filed Aug. 4, 2017 and is incorporated by reference in itsentirety.

FIELD OF THE INVENTION

The present invention relates to a dual catalyst system and processesfor use thereof. In particular, the catalyst system includes anunbridged group 4 metallocene compound, an additional unbridged group 4metallocene compound having a structure different than the firstunbridged group 4 metallocene compound, a support material, and anactivator. The catalyst system may be used for olefin polymerizationprocesses.

BACKGROUND OF THE INVENTION

Polyolefins are widely used commercially because of their robustphysical properties. For example, various types of polyethylenes,including high density, low density, and linear low densitypolyethylenes, are some of the most commercially useful. Polyolefins aretypically prepared with a catalyst that polymerizes olefin monomers.

Low density polyethylene is generally prepared at high pressure usingfree radical initiators. Low density polyethylene typically has adensity at about 0.916-0.930 g/cm³. Typical low density polyethyleneproduced using free radical initiators is known in the industry as“LDPE.” LDPE is also known as “branched” or “heterogeneously branched”polyethylene because of the relatively large number of long chainbranches extending from the main polymer backbone. Polyethylene with asimilar density that does not contain long chain branches is known as“linear low density polyethylene” (“LLDPE”) and is typically producedwith conventional Ziegler-Natta catalysts or with metallocene catalysts.“Linear” means that the polyethylene has few, if any, long chainbranches and typically has a g′vis value of 0.97 or above, such as 0.98or above. Polyethylenes having still greater density are the highdensity polyethylenes (“HDPEs”), e.g., polyethylenes having densitiesgreater than 0.940 g/cm³ and are generally prepared with Ziegler-Nattaor chrome catalysts. Very low density polyethylenes (“VLDPEs”) can beproduced by a number of different processes yielding polyethylenestypically having a density 0.890 to 0.915 g/cm³.

Copolymers of polyolefins, such as polyethylene, have a comonomer, suchas hexene, incorporated into the polyethylene backbone. These copolymersprovide varying physical properties compared to polyethylene alone andare typically produced in a low pressure reactor, utilizing, forexample, solution, slurry, or gas phase polymerization processes.Polymerization may take place in the presence of catalyst systems suchas those employing a Ziegler-Natta catalyst, a chromium based catalyst,or a metallocene catalyst.

A copolymer composition has a composition distribution, which refers tothe distribution of comonomer in the copolymer, typically along thecopolymer backbone. When the amount of comonomer varies among thecopolymer molecules, the composition is said to have a “broad”composition distribution. When the amount of comonomer per 1000 carbonsis similar among the copolymer molecules of different chain lengths, thecomposition distribution is said to be “narrow.”

The composition distribution influences the properties of a copolymercomposition, for example, stiffness, toughness, environmental stresscrack resistance, and heat sealing, among other properties. Thecomposition distribution of a polyolefin composition may be readilymeasured by, for example, Temperature Rising Elution Fractionation(TREF) or Crystallization Analysis Fractionation (CRYSTAF).

A composition distribution of a copolymer composition is influenced bythe identity of the catalyst used to form the polyolefins of thecomposition. Ziegler-Natta catalysts and chromium based catalystsproduce compositions with broad composition distributions, whereasmetallocene catalysts typically produce compositions with narrowcomposition distributions.

Furthermore, polyolefins, such as polyethylenes, which have highmolecular weight, generally have desirable mechanical properties overtheir lower molecular weight counterparts. However, high molecularweight polyolefins can be difficult to process and can be costly toproduce. Polyolefin compositions having a bimodal molecular weightdistribution are desirable because they can combine the advantageousmechanical properties of a high molecular weight fraction of thecomposition with the improved processing properties of a low molecularweight fraction of the composition. Unless otherwise indicated, as usedherein, “high molecular weight” is defined as a weight average molecularweight (Mw) value of 150,000 g/mol or more. “Low molecular weight” isdefined as an Mw value of less than 150,000 g/mol.

For example, useful bimodal polyolefin compositions include a firstpolyolefin having low molecular weight and high comonomer content (i.e.,comonomer incorporated into the polyolefin backbone) while a secondpolyolefin has a high molecular weight and low comonomer content. Asused herein, “low comonomer content” is defined as a polyolefin having 6wt % or less of comonomer based upon the total weight of the polyolefin.The high molecular weight fraction produced by the second catalystcompound may have a high comonomer content. As used herein, “highcomonomer content” is defined as a polyolefin having greater than 6 wt %of comonomer based upon the total weight of the polyolefin.

There are several methods for producing bimodal or broad molecularweight distribution polyolefins, e.g., melt blending, polymerization inreactors in series or parallel configuration, or single reactor withbimetallic catalysts. However, these methods, such as melt blending,suffer from the disadvantages brought by the need for completehomogenization of polyolefin compositions and high cost.

Furthermore, synthesizing these bimodal polyolefin compositions in amixed catalyst system would involve a first catalyst to catalyze thepolymerization of, for example, ethylene under substantially similarconditions as that of a second catalyst while not interfering with thecatalysis of polymerization of the second catalyst. For example, twodifferent metallocene catalysts may interfere with the polymerizationcatalysis of each other, resulting in reduced catalytic activity,reduced molecular weight polyolefins, and reduced comonomerincorporation.

There exists a need for catalyst systems that provide polyolefincompositions having novel combinations of comonomer content fractionsand molecular weights. There is further a need for novel catalystsystems where a first catalyst does not negatively impact thepolymerization catalysis of a second catalyst or vice versa.

Useful catalysts for olefin polymerization are often based oncyclopentadienyl transition metal catalyst compounds (metallocenes) ascatalyst precursors combined with activators, typically an alumoxane orwith an activator containing a non-coordinating anion. A typicalmetallocene catalyst system includes metallocene catalyst, activator,and optional support. Supported catalyst systems are used in manypolymerization processes, often in slurry or gas phase polymerizationprocesses.

Catalysts for olefin polymerization are often based on substitutedmetallocenes as catalyst precursors, which are activated either with thehelp of an alumoxane, or with an activator containing a non-coordinatinganion.

For example U.S. Pat. No. 7,829,495 disclosesMe₂Si(fluorenyl)(3-nPr-Cp)ZrCl₂ and U.S. Pat. No. 7,179,876 disclosessupported (nPrCp)₂HfMe₂.

Likewise, Me₂C(Cp)(Me₃SiCH₂—Ind)MCl₂ and Me₂C(Cp)(Me, Me₃SiCH₂—Ind)MCl₂,where M is Zr or Hf have been synthesized and screened for thesyndiospecific polymerization of propylene; see Leino, R., Gomez, F.;Cole, A.; Waymouth, R. Macromolecules 2001, 34, 2072-2082.

Additional references of interest include: Hong et al. in ImmobilizedMe₂Si(C₅Me₄)(N-t-Bu)TiCl₂/(nBuCp)₂ZrCl₂ Hybrid Metallocene CatalystSystem for the Production of Poly(ethylene-co-hexene) withPseudo-bimodal Molecular Weight and Inverse Comonomer Distribution,(Polymer Engineering and Science-2007, DOI 10.1002/pen, pages 131-139,published online in Wiley InterScience (www.interscience.wiley.com) 2007Society of Plastics Engineers); Kim, J. D. et al., J. Polym. Sci. PartA: Polym Chem., 38, 1427 (2000); Iedema, P. D. et al., Ind. Eng. Chem.Res., 43, 36 (2004); U.S. Pat. Nos. 4,701,432; 5,032,562; 5,077,255;5,135,526; 5,183,867; 5,382,630; 5,382,631; 5,516,848; 5,525,678;6,069,213; 6,207,606; 6,380,311; 6,656,866; 6,828,394; 6,964,937;6,956,094; 6,995,109; 7,041,617; 7,119,153; 7,129,302; 7,141,632;7,172,987; 7,179,876; 7,192,902; 7,199,072; 7,199,073; 7,226,886;7,285,608; 7,312,283; 7,355,058; 7,385,015; 7,396,888; 7,547,754;7,572,875; 7,595,364; 7,619,047; 7,625,982; 7,662,894; 7,829,495;7,855,253; 8,088,867; 8,110,518; 8,138,113; 8,268,944; 8,288,487;8,329,834; 8,378,029; 8,383,754; 8,575,284; 8,598,061; 8,680,218;8,785,551; 8,815,357; 8,846,841; 8,940,842; 8,957,168; 9,006,367;9,079,993; 9,096,745; 9,163,098; 9,181,370; 9,217,049; 9,303,099;9,447,265; U.S. Publications 2004/259722; 2006/275571; 2012/130032;2014/031504; 2014/127427; 2015/322184; 2015/299352; 2016/032027;2016/075803; 2017/114167; PCT Publications WO 97/35891; WO 98/49209; WO00/12565; WO 2001/09200; WO 02/060957; WO 2004/046214; WO 2006/080817;WO 2007/067259; WO 2007/080365; WO 2009/146167; WO 2012/006272; WO2012/158260; WO 2015/123168; WO 2016/172099; WO 2016/171807; WO2016/171810; EP 2 374 822; EP 2 003 166; EP 0 729 387; EP 0 676 418; EP0 705 851; KR 20150058020; KR 101132180; Sheu, S., 2006, “Enhancedbimodal PE makes the impossible possible”,http://www.tappi.org/content/06asiaplace/pdfs-english/enhanced.pdf; Chenet al., “Modeling and Simulation of Borstar Bimodal Polyethylene ProcessBased on Rigorous PC-SAFT Equation of State Model”, Industrial &Engineering Chemical Research, 53, pp. 19905-19915, (2014); A. Calhoun,et al. “Polymer Chemistry”, Chapter 5, pages 77-87; and Stadelhofer, etal., J. Organomet. Chem, 1975, 84, pp. C₁-C₄.

There is still a need in the art for new and improved catalyst systemsfor the polymerization of olefins, in order to achieve increasedactivity or enhanced polymer properties, to increase conversion orcomonomer incorporation, or to alter comonomer distribution. There isalso a need for supported catalyst systems and processes for thepolymerization of olefins (such as ethylene) using such catalyst systemsto provide ethylene polymers having the unique properties of highstiffness, high toughness and good processability.

SUMMARY OF THE INVENTION

The present invention relates to a supported catalyst system includingan unbridged group 4 metallocene compound; an additional unbridged group4 metallocene compound having a structure different than the firstmetallocene compound; a support material; and an activator; wherein thefirst unbridged group 4 metallocene compound is represented by theformula (A):

whereM* is a group 4 metaleach of R¹, R², R⁴ and R⁵ is independently hydrogen, alkoxide, or C₁ toC₄₀ substituted or unsubstituted hydrocarbyl;R³ is independently hydrogen, alkoxide, C₁ to C₄₀ substituted orunsubstituted hydrocarbyl, or —R¹¹—SiR′₃ or —R¹¹—CR′₃ where R¹¹ is C₁ toC₄ hydrocarbyl, and each R′ is independently C₁ to C₂₀ substituted orunsubstituted hydrocarbyl;each R⁶, R⁷, R⁸, and R¹⁰ is independently hydrogen, halide, alkoxide, orC₁ to C₄₀ substituted or unsubstituted hydrocarbyl;R⁹ is —R¹¹—SiR′₃ or —R¹¹—CR′₃ where R¹¹ is C₁ to C₄ hydrocarbyl, andeach R′ is independently C₁ to C₂₀ substituted or unsubstitutedhydrocarbyl; andeach X is independently a univalent anionic ligand, or two Xs are joinedto form a metallocyclic ring, or two Xs are joined to form a chelatingligand, a diene ligand, or an alkylidene ligand; andthe second unbridged group 4 metallocene compound is represented byformula (B):Cp_(m)MX′_(q)  (B)wherein each Cp is independently substituted or unsubstitutedcyclopentadienyl, indenyl or fluorenyl, M is zirconium or hafnium, X′ isa leaving group, such as a halide, hydride, alkyl, alkenyl or arylalkyl,and m=2 or 3, q=0, 1, 2, or 3, and the sum of m+q is equal to theoxidation state of the transition metal, typically 2, 3, or 4,preferably 4, and each Cp and X′ is bound to M.

The present invention also provides a process for polymerization ofmonomers (such as olefin monomers) comprising contacting one or moremonomers with the above supported catalyst systems.

The present invention also provides a process to produce ethylenepolymer compositions comprising: i) contacting in a single reactionzone, in the gas phase or slurry phase, ethylene and C₃ to C₂₀ comonomerwith a catalyst system comprising a support, an activator, and thecatalyst system described above, and ii) obtaining an in-situ ethylenepolymer composition having at least 50 mol % ethylene and a density of0.91 g/cc or more, alternatively 0.935 g/cc or more.

The present invention also provides a process to produce ethylenepolymer compositions comprising: i) contacting in a single reactionzone, in the gas phase or slurry phase, ethylene and C₃ to C₂₀ comonomerwith a catalyst system comprising a support, an activator, and thecatalyst system described above, and obtaining an ethylene polymerhaving: a) an RCI,m greater than 20 and less than 35, and an Mw/Mn of 3to 4; or b) an RCI,m greater than 50 and an Mw/Mn of greater than 5.

The present invention also provides polymer compositions produced by themethods and catalyst systems described herein.

DETAILED DESCRIPTION

The present invention provides a dual catalyst systems and processes foruse thereof. In particular, the catalyst system comprises an unbridgedgroup 4 metallocene compound, an additional unbridged group 4metallocene compound having a structure different than the firstunbridged group 4 metallocene compound, a support material, and anactivator. The catalyst system may be used for olefin polymerizationprocesses. Catalyst systems of the present invention can provideincreased activity or enhanced polymer properties, to increaseconversion or comonomer incorporation, or to alter comonomerdistribution. Catalyst systems and processes of the present inventioncan provide ethylene polymers having the unique properties of highstiffness, high toughness and good processability.

For purposes of the present invention, a “catalyst system” is acombination of at least two catalyst compounds, an activator, and asupport material. The catalyst systems may further comprise one or moreadditional catalyst compounds. The terms “mixed catalyst system,” “dualcatalyst system,” “mixed catalyst,” and “supported catalyst system” maybe used interchangeably herein with “catalyst system.” For purposes ofthe present invention, when catalyst systems are described as comprisingneutral stable forms of the components, it is well understood by one ofordinary skill in the art, that the ionic form of the component is theform that reacts with the monomers to produce polymers.

As used in this specification and the claims thereto, the term“metallocene compound” includes compounds having two or three Cp ligands(cyclopentadienyl and ligands isolobal to cyclopentadienyl) bound to atleast one Zr or Hf metal atom, and one or more leaving group(s) bound tothe at least one metal atom.

For purposes of the present disclosure and claims thereto, in relationto all metallocene catalyst compounds, the term “substituted” means thata hydrogen group has been replaced with a hydrocarbyl group, aheteroatom, or a heteroatom containing group. For example, methylcyclopentadiene (Cp) is a Cp substituted with a methyl group.

For purposes of the present disclosure, the term “alkoxide(s)” includesthose where the alkyl group is a C₁ to C₁₀ hydrocarbyl. The alkyl groupmay be straight chain, branched, or cyclic. The alkyl group may besaturated or unsaturated. In some embodiments, the alkyl group maycomprise at least one aromatic group.

The term “complex” is used to describe molecules in which an ancillaryligand is coordinated to a central transition metal atom. The ligand isbulky and stably bonded to the transition metal so as to maintain itsinfluence during use of the catalyst, such as polymerization. The ligandmay be coordinated to the transition metal by covalent bond and/orelectron donation coordination or intermediate bonds. The transitionmetal complexes are generally subjected to activation to perform theirpolymerization function using an activator which is believed to create acation as a result of the removal of an anionic group, often referred toas a leaving group, from the transition metal. “Complex,” as usedherein, is also often referred to as “catalyst precursor,”“pre-catalyst,” “catalyst,” “catalyst compound,” “metal compound,”“metal catalyst compound”, “transition metal compound,” or “transitionmetal complex.” These words are used interchangeably. “Activator” and“cocatalyst” are also used interchangeably.

The terms “hydrocarbyl radical,” “hydrocarbyl” and “hydrocarbyl group”are used interchangeably throughout this document. Likewise the terms“group,” “radical,” and “substituent” are also used interchangeably inthis document. For purposes of the present invention, “hydrocarbylradical” is defined to be C₁-C₁₀₀ radicals, that may be linear,branched, or cyclic, and when cyclic, aromatic or non-aromatic.

For purposes of the present invention, unless otherwise indicated, theterm “substituted” means that a hydrogen group has been replaced with aheteroatom, or a heteroatom containing group. For example, substitutedhydrocarbyl radicals are radicals in which at least one hydrogen atom ofthe hydrocarbyl radical has been substituted with at least onefunctional group such as Cl, Br, F, I, NR*₂, OR*, SeR*, TeR*, PR*₂,AsR*₂, SbR*₂, SR*, BR*₂, SiR*₃, GeR*₃, SnR*₃, PbR*₃, and the like (whereR* is H or a C₁ to C₂₀ hydrocarbyl group), or where at least oneheteroatom has been inserted within a hydrocarbyl ring.

The term “ring atom” means an atom that is part of a cyclic ringstructure. By this definition, a benzyl group has six ring atoms andtetrahydrofuran has 5 ring atoms.

A “ring carbon atom” is a carbon atom that is part of a cyclic ringstructure. By this definition, a benzyl group has six ring carbon atomsand para-methylstyrene also has six ring carbon atoms.

The term “aryl” or “aryl group” means a six carbon aromatic ring and thesubstituted variants thereof, including but not limited to, phenyl,2-methyl-phenyl, xylyl, 4-bromo-xylyl. Likewise, heteroaryl means anaryl group where a ring carbon atom (or two or three ring carbon atoms)has been replaced with a heteroatom, preferably, N, O, or S.

The term “arylalky” is an aryl-substituted alkyl radical and may be usedinterchangeably with the term “aralkyl.” Examples of aralkyl includebenzyl, diphenylmethyl, triphenylmethyl, phenylethyl, and diphenylethyl.

A “heterocyclic ring” is a ring having a heteroatom in the ringstructure as opposed to a heteroatom substituted ring where a hydrogenon a ring atom is replaced with a heteroatom. For example,tetrahydrofuran is a heterocyclic ring and 4-N,N-dimethylamino-phenyl isa heteroatom substituted ring.

As used herein the term “aromatic” also refers to pseudoaromaticheterocycles which are heterocyclic substituents that have similarproperties and structures (nearly planar) to aromatic heterocyclicligands, but are not by definition aromatic; likewise, the term aromaticalso refers to substituted aromatics.

The term “continuous” means a system that operates without interruptionor cessation. For example, a continuous process to produce a polymerwould be one where the reactants are continually introduced into one ormore reactors and polymer product is continually withdrawn.

As used herein, the numbering scheme for the Periodic Table groups isthe new notation as set out in Chemical and Engineering News, 63(5), 27,(1985).

An “olefin,” is a linear, branched, or cyclic compound of carbon andhydrogen having at least one double bond. For purposes of thisspecification and the claims appended thereto, when a polymer orcopolymer is referred to as comprising an olefin, the olefin present insuch polymer or copolymer is the polymerized form of the olefin. Forexample, when a copolymer is said to have an “ethylene” content of 35 wt% to 55 wt %, it is understood that the mer unit in the copolymer isderived from ethylene in the polymerization reaction and said derivedunits are present at 35 wt % to 55 wt %, based upon the weight of thecopolymer. A “polymer” has two or more of the same or different merunits. A “homopolymer” is a polymer having mer units that are the same.A “copolymer” is a polymer having two or more mer units that aredifferent from each other. “Different” as used to refer to mer unitsindicates that the mer units differ from each other by at least one atomor are different isomerically. Accordingly, the definition of copolymer,as used herein, includes terpolymers and the like. An “ethylene polymer”or “ethylene copolymer” is a polymer or copolymer comprising at least 50mol % ethylene derived units, a “propylene polymer” or “propylenecopolymer” is a polymer or copolymer comprising at least 50 mol %propylene derived units, and so on.

For purposes of the present invention, an ethylene polymer having adensity of 0.86 g/cm³ or less is referred to as an ethylene elastomer orelastomer; an ethylene polymer having a density of more than 0.86 toless than 0.910 g/cm³ is referred to as an ethylene plastomer orplastomer; an ethylene polymer having a density of 0.910 to 0.940 g/cm³is referred to as a low density polyethylene; and an ethylene polymerhaving a density of more than 0.940 g/cm³ is referred to as a highdensity polyethylene (HDPE). Density is determined according to ASTM D1505 using a density-gradient column on a compression-molded specimenthat has been slowly cooled to room temperature (i.e., over a period of10 minutes or more) and allowed to age for a sufficient time that thedensity is constant within +/−0.001 g/cm³).

Polyethylene in an overlapping density range, i.e., 0.890 to 0.930g/cm³, typically from 0.915 to 0.930 g/cm³, which is linear and does notcontain long chain branching is referred to as “linear low densitypolyethylene” (LLDPE) and has been produced with conventionalZiegler-Natta catalysts, vanadium catalysts, or with metallocenecatalysts in gas phase reactors and/or in slurry reactors and/or insolution reactors. “Linear” means that the polyethylene has no longchain branches, typically referred to as a branching index (g′_(vis)) of0.97 or above, preferably 0.98 or above. Branching index, g′_(vis), ismeasured by GPC-4D as described below.

For purposes of the present invention, ethylene shall be considered analpha-olefin (α-olefin).

As used herein, M_(n) is number average molecular weight, M_(w) isweight average molecular weight, and M_(z) is z average molecularweight, wt % is weight percent, and mol % is mole percent. Unlessotherwise noted, all average molecular weights (e.g., Mw, Mn, Mz) arereported in units of g/mol. Molecular weight distribution (MWD), alsoreferred to as polydispersity index (PDI), is defined to be Mw dividedby Mn.

The following abbreviations may be used herein: Me is methyl, Et isethyl, t-Bu and tBu are tertiary butyl, iPr and ^(i)Pr are isopropyl, Cyis cyclohexyl, THF (also referred to as thf) is tetrahydrofuran, Bn isbenzyl, Ph is phenyl, Cp is cyclopentadienyl, Cp* is pentamethylcyclopentadienyl, Ind is indenyl, Flu is fluorenyl, and MAO ismethylalumoxane.

The present invention provides a supported catalyst system comprising:(i) a first unbridged metallocene compound; (ii) a second unbridgedmetallocene compound; (iii) a support material; and (iv) an activator;wherein the first unbridged metallocene compound is represented byformula (A):

whereM* is a group 4 metal, preferably Hf;each of R¹, R², R⁴, and R⁵ is independently hydrogen, alkoxide, or C₁ toC₄₀ substituted or unsubstituted hydrocarbyl;R³ is independently hydrogen, alkoxide, C₁ to C₄₀ substituted orunsubstituted hydrocarbyl, or —R¹¹—SiR′₃ or —R¹¹—CR′₃ where R¹¹ is a C₁to C₄ hydrocarbyl, and each R′ is independently C₁ to C₂₀ substituted orunsubstituted hydrocarbyl;each R⁶, R⁷, R⁸, and R¹⁰ is independently hydrogen, halide, alkoxide, orC₁ to C₄₀ substituted or unsubstituted hydrocarbyl;R⁹ is —R¹¹—SiR′₃ or —R¹¹—CR′₃ where R¹¹ is a C₁ to C₄ hydrocarbyl, andeach R′ is independently C₁ to C₂₀ substituted or unsubstitutedhydrocarbyl; andeach X is independently a univalent anionic ligand, or two Xs are joinedto form a metallocyclic ring, or two Xs are joined to form a chelatingligand, a diene ligand, or an alkylidene ligand; andthe second unbridged metallocene compound represented by formula (B):Cp_(m)MX′_(q)  (B)wherein each Cp is independently substituted or unsubstitutedcyclopentadienyl, indenyl or fluorenyl, M is zirconium or hafnium(preferably Zr), X′ is a leaving group, such as a halide, hydride,alkyl, alkenyl or arylalkyl, and m=2 or 3, q=0, 1, 2, or 3, and the sumof m+q is equal to the oxidation state of the transition metal, and eachCp and X′ is bound to M.

The present invention further provides a process for polymerization ofolefin monomers comprises contacting one or more monomers with the abovesupported catalyst systems.

The above two catalyst components can have different hydrogen responses(each having a different reactivity toward hydrogen) during thepolymerization process. Hydrogen is often used in olefin polymerizationto control the final properties of the polyolefin. The first catalystcomponent can show a more negative response to changes of hydrogenconcentration in reactor than the second catalyst component. Owing tothe differing hydrogen response of the catalyst components in thesupported catalyst systems, the properties of resulting polymer arecontrollable. Changes of hydrogen concentration in the reactor mayaffect molecular weight, molecular weight distributions, and otherproperties of the resulting polyolefin when using a combination of suchtwo catalyst components. Thus, the present invention further provides amulti-modal polyolefin obtained from polymerizations using the abovesupported catalyst systems.

In useful embodiments, catalyst A is a good comonomer (such as hexene)incorporator (e.g., provides comonomer content of 6% or greater) andyields polyethylene with higher molecular weight than catalyst B whichunder similar conditions yields lower molecular weight than catalyst A.Catalyst B can also incorporate less comonomer (such as hexene) undersimilar reaction conditions. When catalyst A and catalyst B are combinedon one support, an in-reactor blend (also referred to as an in-situblend) of polyethylene is produced with a mix of low and high densityresins in which the higher density resin (typically having a highermelting point) is combined with lower density, higher molecular weightresin. Catalyst A may be a single isomer or a combination of isomers,e.g., 2, 3, 4, 5, or 6 isomers, typically 2 isomers. Catalyst B may be asingle isomer or a combination of isomers, e.g., 2, 3, 4, 5, or 6isomers, typically 2 isomers.

The two transition metal compounds may be used in any ratio. Preferredmolar ratios of (A) the first unbridged transition metal catalyst to (B)the second unbridged transition metal catalyst fall within the range of(A):(B) 1:1000 to 1000:1, alternatively 1:100 to 500:1, alternatively1:10 to 200:1, alternatively 1:1 to 100:1, and alternatively 1:1 to75:1, and alternatively 5:1 to 50:1. The particular ratio chosen willdepend on the exact catalyst compounds chosen, the method of activation,and the end product desired. In a particular embodiment, when using thetwo catalyst compounds, where both are activated with the sameactivator, useful mole percents, based upon the molecular weight of thecatalyst compounds, are (10 to 99.9% A):(0.1 to 90% B), alternatively(25 to 99% A):(0.5 to 50% B), alternatively (50 to 99% A):(1 to 25% B),and alternatively (75 to 99% A):(1 to 10% B).

For purposes of the present invention, one metallocene catalyst compoundis considered different from another if they differ by at least oneatom. For example “bisindenyl zirconium dichloride” is different from“(indenyl)(2-methylindenyl) zirconium dichloride” which is differentfrom “(indenyl)(2-methylindenyl) hafnium dichloride.” Catalyst compoundsthat differ only by isomer are considered the same for purposes of thepresent invention, e.g., rac-bis(1-methylindenyl)hafnium dimethyl isconsidered to be the same as meso-bis(1-methyl-indenyl)hafnium dimethyl.Thus, as used herein, a single metallocene catalyst component having aracemic and/or meso isomer does not, itself, constitute two differentmetallocene catalyst components.

The present invention provides a process to produce ethylene polymercompositions comprising: i) contacting in a single reaction zone, in thegas phase or slurry phase, ethylene and C₃ to C₂₀ comonomer with acatalyst system comprising a support, an activator, and the catalystsdescribed above, and obtaining an ethylene polymer having: a) an RCI,mgreater than 30 and an Mw/Mn of greater than 3; or b) an RCI,m greaterthan 50 and an Mw/Mn of greater than 5. Without wishing to be bound bytheory, it is believed that the ethylene polymer produced herein (i.e.,an in-situ ethylene polymer composition) has at least two polymercomponents where the first component is derived from the catalystrepresented by formula A and has more comonomer (such as hexene) andhigher Mw as compared to the second component derived from the catalystrepresented by formula B which has less comonomer (such as hexene) andlower Mw as compared to the first component as determined by 4D GPC.

The First Unbridged Metallocene

In at least one embodiment, the supported catalyst systems comprise atransition metal complex represented by formula (A):

whereM* is a group 4 metal, such as Zr, Hf, or Ti, most preferably Hf;each of R¹, R², R⁴, and R⁵ is independently hydrogen, alkoxide, or C₁ toC₄₀ substituted or unsubstituted hydrocarbyl;R³ is independently hydrogen, alkoxide, C₁ to C₄₀ substituted orunsubstituted hydrocarbyl, or —R¹¹—SiR′₃ or —R¹¹—CR′₃ where R¹¹ is a C₁to C₄ hydrocarbyl, and each R′ is independently C₁ to C₂₀ substituted orunsubstituted hydrocarbyl;each R⁶, R⁷, R⁸, and R¹⁰ is independently hydrogen, halide, alkoxide, orC₁ to C₄₀ substituted or unsubstituted hydrocarbyl;R⁹ is —R¹¹—SiR′₃ or —R¹¹—CR′₃ where R¹¹ and R′ are defined above; andeach X is independently a univalent anionic ligand, or two Xs are joinedto form a metallocyclic ring, or two Xs are joined to form a chelatingligand, a diene ligand, or an alkylidene ligand.

In a preferred embodiment, each R¹, R², R⁴ and R⁵ is independentlyhydrogen, or a substituted C₁ to C₁₂ hydrocarbyl group or anunsubstituted C₁ to C₁₂ hydrocarbyl group, preferably each R¹, R², R⁴and R⁵ is independently a C₁ to C₂₀ alkyl group), preferably hydrogen,methyl, ethyl, propyl, butyl, pentyl, hexyl, or an isomer thereof,preferably hydrogen or methyl.

In a preferred embodiment, R³ is hydrogen, or a substituted C₁ to C₁₂hydrocarbyl group or an unsubstituted C₁ to C₁₂ hydrocarbyl group,preferably R³ is a C₁ to C₂₀ alkyl group, preferably hydrogen, methyl,ethyl, propyl, butyl, pentyl, hexyl, or an isomer thereof, preferablyhydrogen or methyl, or R³ is —R²⁰—SiR′₃ or is —R²⁰—CR′₃ where R²⁰ ishydrogen or a C₁ to C₄ hydrocarbyl (preferably CH₂; CH₂CH₂, (Me)CHCH₂,(Me)CH), and each R′ is independently hydrogen or a C₁ to C₂₀substituted or unsubstituted hydrocarbyl, preferably a substituted C₁ toC₁₂ hydrocarbyl group or an unsubstituted C₁ to C₁₂ hydrocarbyl group,preferably methyl, ethyl, propyl, butyl, pentyl, hexyl, phenyl,biphenyl, or an isomer thereof, R′ is a C₁ to C₂₀ alkyl or aryl, such asmethyl, methyl phenyl, phenyl, biphenyl, pentamethylphenyl,tetramethylphenyl, or di-t-butylphenyl, provided that at least one R′ isnot H, alternatively 2 of R′ are not H, alternatively 3 of R′ are not H.

Alternatively, R³ is —CH₂—SiMe₃, —CH₂—SiEt₃, —CH₂—SiPr₃, —CH₂—SiBu₃,—CH₂—SiCy₃, —CH₂—C(CH₃)₃, —CH₂—CH(CH₃)₂, —CH₂CPh₃, —CH₂(C₆Me₅),—CH₂—C(CH₃)₂Ph, —CH₂—C(Cy)Ph₂. —CH₂—SiH(CH₃)₂, —CH₂SiPh₃,—CH₂—Si(CH₃)₂Ph, —CH₂—Si(CH₃)₂Ph, —CH₂—Si(CH₃)Ph₂, —CH₂—Si(Et)₂Ph,—CH₂—Si(Et)Ph₂, —CH₂—Si(CH₂)₃Ph, —CH₂—Si(CH₂)₄Ph, —CH₂—Si(Cy)Ph₂, or—CH₂—Si(Cy)₂Ph.

Alternatively, each of R¹, R², R³, and R⁴ is not H.

In a preferred embodiment, each R⁶, R⁷, R⁸, and R¹⁰ is independentlyhydrogen, or a substituted C₁ to C₁₂ hydrocarbyl group or anunsubstituted C₁ to C₁₂ hydrocarbyl group, preferably a C₁ to C₂₀ alkylgroup, preferably hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl,or an isomer thereof, preferably a hydrogen or methyl.

In a preferred embodiment, R⁹ is —R²⁰—SiR′₃ or is —R²⁰—CR′₃ where R²⁰ isa C₁ to C₄ hydrocarbyl (preferably —CH₂—, —CH₂CH₂—, -(Me)CHCH₂—,-(Me)CH—, and each R′ is independently hydrogen or a C₁ to C₂₀substituted or unsubstituted hydrocarbyl, preferably a substituted C₁ toC₁₂ hydrocarbyl group or an unsubstituted C₁ to C₁₂ hydrocarbyl group,preferably methyl, ethyl, propyl, butyl, pentyl, hexyl, phenyl,biphenyl, or an isomer thereof, R′ is a C₁ to C₂₀ alkyl or aryl, such asmethyl, methyl phenyl, phenyl, biphenyl, pentamethylphenyl,tetramethylphenyl, or di-t-butylphenyl, provided that at least one R′ isnot H, alternatively 2 of R′ are not H, alternatively 3 of R′ are not H;

Alternatively, R⁹ is —CH₂—SiMe₃, —CH₂—SiEt₃, —CH₂—SiPr₃, —CH₂—SiBu₃,—CH₂—SiCy₃, —CH₂(C₆Me₅), —CH₂—C(CH₃)₂Ph, —CH₂—C(Cy)Ph₂. —CH₂—SiH(CH₃)₂,—CH₂SiPh₃, —CH₂—Si(CH₃)₂Ph, —CH₂—Si(CH₃)Ph₂, —CH₂—Si(Et)₂Ph,—CH₂—Si(Et)Ph₂, —CH₂—Si(CH₂)₃Ph, —CH₂—Si(CH₂)₄Ph, —CH₂—Si(Cy)Ph₂, or—CH₂—Si(Cy)₂Ph.

Alternatively, R³ and R⁹ are independently —R²⁰—SiR′₃ or is —R²⁰—CR′₃where R²⁰ is a C₁ to C₄ hydrocarbyl (preferably —CH₂—, —CH₂CH₂—,-(Me)CHCH₂—, -(Me)CH—, and each R′ is independently hydrogen, or a C₁ toC₂₀ substituted or unsubstituted hydrocarbyl, preferably a substitutedC₁ to C₁₂ hydrocarbyl group or an unsubstituted C₁ to C₁₂ hydrocarbylgroup, preferably methyl, ethyl, propyl, butyl, pentyl, hexyl, phenyl,biphenyl, or an isomer thereof, R′ is a C₁ to C₂₀ alkyl or aryl, such asmethyl, methyl phenyl, phenyl, biphenyl, pentamethylphenyl,tetramethylphenyl, or di-t-butylphenyl; alternatively R³ and R⁹ areselected from the group consisting of: —CH₂—SiMe₃, —CH₂—SiEt₃,—CH₂—SiPr₃, —CH₂—SiBu₃, —CH₂—SiCy₃, —CH₂—C(CH₃)₃, —CH₂—CH(CH₃)₂,—CH₂CPh₃, —CH₂(C₆Me₅), —CH₂—C(CH₃)₂Ph, —CH₂—C(Cy)Ph₂. —CH₂—SiH(CH₃)₂,—CH₂SiPh₃, —CH₂—Si(CH₃)₂Ph, —CH₂—Si(CH₃)Ph₂, —CH₂—Si(Et)₂Ph,—CH₂—Si(Et)Ph₂, —CH₂—Si(CH₂)₃Ph, —CH₂—Si(CH₂)₄Ph, —CH₂—Si(Cy)Ph₂, or—CH₂—Si(Cy)₂Ph.

Alternatively, each X may be, independently, a halide, a hydride, analkyl group, an alkenyl group or an arylalkyl group.

Alternatively, each X is independently selected from the groupconsisting of hydrocarbyl radicals having from 1 to 20 carbon atoms,aryls, hydrides, amides, alkoxides, sulfides, phosphides, halides,dienes, amines, phosphines, ethers, and a combination thereof, (two Xsmay form a part of a fused ring or a ring system), preferably each X isindependently selected from halides, aryls and C₁ to C₅ alkyl groups,preferably each X is a phenyl, methyl, ethyl, propyl, butyl, pentyl, orchloro group.

Useful asymmetric catalysts are preferably such that a mirror plane cannot be drawn through the metal center and the cyclopentadienyl moietiesbridged to the metal center are structurally different.

Catalyst compounds represented by formula (A) can be one or more of:(Cp)(3-CH₂—SiMe₃-Cp)HfMe₂; (MeCp)(3-CH₂—SiMe₃-Cp)HfMe₂;(EtCp)(3-CH₂—SiMe₃₋Cp)HfMe₂; (PrCp)(3-CH₂—SiMe₃-Cp)HfMe₂;(BuCp)(3-CH₂—SiMe₃-Cp)HfMe₂; (BzCp)(3-CH₂—SiMe₃-Cp)HfMe₂;(3-CH₂—SiMe₃-Cp)₂HfMe₂; (Me₃Cp)(3-CH₂—SiMe₃-Cp)HfMe₂;(Me₄Cp)(3-CH₂—SiMe₃-Cp)HfMe₂; (Me₅Cp)(3-CH₂—SiMe₃-Cp)HfMe₂; (1-Me,3-Bu-Cp)(3-CH₂—SiMe₃-Cp)HfMe₂; (1-Me, 3-Ph-Cp)(3-CH₂—SiMe₃-Cp)HfMe₂;(Me₄Cp-Pr)(3-CH₂—SiMe₃₋Cp)HfMe₂; (Me₄Cp-CH₂—SiMe₃)(3-CH₂—SiMe₃-Cp)HfMe₂;(2-Me, 3-CH₂—SiMe₃-Ind)₂HfMe₂; (2-Et, 3-CH₂—SiMe₃-Ind)₂HfMe₂; (2-Pr,3-CH₂—SiMe₃-Ind)₂HfMe₂; (2-Bu, 3-CH₂—SiMe₃-Ind)₂HfMe₂; (2-Ph,3-CH₂—SiMe₃-Ind)₂HfMe₂; (3-CH₂—SiMe₃-Ind)₂HfMe₂;(3-CH₂—SiMe₃-Ind)(3-CH₂—SiMe₃-Cp)HfMe₂; (3-Me-Ind)(3-CH₂—SiMe₃-Cp)HfMe₂;(3-Et-Ind)(3-CH₂—SiMe₃-Cp)HfMe₂; (3-Pr-Ind)(3-CH₂—SiMe₃-Cp)HfMe₂;(3-Bu-Ind)(3-CH₂—SiMe₃-Cp)HfMe₂; (Cp)(3-CH₂—SiMe₃-Ind)HfMe₂;(MeCp)(3-CH₂—SiMe₃-Ind)HfMe₂; (EtCp)(3-CH₂—SiMe₃-Ind)HfMe₂;(PrCp)(3-CH₂—SiMe₃-Ind)HfMe₂; (BuCp)(3-CH₂—SiMe₃-Ind)HfMe₂;(Me₃Cp)(3-CH₂—SiMe₃-Ind)HfMe₂; (Me₄Cp)(3-CH₂—SiMe₃-Ind)HfMe₂;(Me₅Cp)(3-CH₂—SiMe₃₋Ind)HfMe₂; (1-Me, 3-Bu-Cp)(3-CH₂—SiMe₃-Ind)HfMe₂;(1-Me, 3-Ph-Cp)(3-CH₂—SiMe₃-Ind)HfMe₂, (Cp)(3-CH₂—SiMe₃-Cp)HfMe₂;(MeCp)(3-CH₂—SiMe₃-Cp)HfMe₂; (EtCp)(3-CH₂—SiMe₃-Cp)HfMe₂;(PrCp)(3-CH₂—SiMe₃-Cp)HfMe₂; (BuCp)(3-CH₂—SiMe₃-Cp)HfMe₂;(BzCp)(3-CH₂—SiMe₃-Cp)HfMe₂; (3-CH₂—SiMe₃-Cp)₂HfMe₂;(Me₂Cp)(3-CH₂—SiMe₃-Cp)HfMe₂; (Me₃Cp)(3-CH₂—SiMe₃-Cp)HfMe₂;(Me₄Cp)(3-CH₂—SiMe₃-Cp)HfMe₂; (Me₅Cp)(3-CH₂—SiMe₃-Cp)HfMe₂;(Et₂Cp)(3-CH₂—SiMe₃-Cp)HfMe₂; (Et₃Cp)(3-CH₂—SiMe₃-Cp)HfMe₂;(Et₄Cp)(3-CH₂—SiMe₃-Cp)HfMe₂; (Et₅Cp)(3-CH₂—SiMe₃-Cp)HfMe₂;(Pr₂Cp)(3—CH₂—SiMe₃-Cp)HfMe₂; (Pr₃Cp)(3-CH₂—SiMe₃-Cp)HfMe₂;(Pr₄Cp)(3-CH₂—SiMe₃-Cp)HfMe₂; (Pr₅Cp)(3-CH₂—SiMe₃-Cp)HfMe₂;(Bu₂Cp)(3-CH₂—SiMe₃-Cp)HfMe₂; (Bu₃Cp)(3-CH₂—SiMe₃-Cp)HfMe₂;(Bu₄Cp)(3-CH₂—SiMe₃-Cp)HfMe₂; (Bu₅Cp)(3-CH₂—SiMe₃-Cp)HfMe₂;(Bz₂Cp)(3-CH₂—SiMe₃-Cp)HfMe₂; (Bz₃Cp)(3-CH₂—SiMe₃-Cp)HfMe₂;(Bz₄Cp)(3-CH₂—SiMe₃-Cp)HfMe₂; (Bz₅Cp)(3-CH₂—SiMe₃-Cp)HfMe₂;(EtMe₄Cp)(3-CH₂—SiMe₃-Cp)HfMe₂; (PrMe₄Cp)(3-CH₂—SiMe₃-Cp)HfMe₂;(BuMe₄Cp)(3-CH₂—SiMe₃-Cp)HfMe₂; (PnMe₄Cp)(3-CH₂—SiMe₃-Cp)HfMe₂;(HxMe₄Cp)(3-CH₂—SiMe₃-Cp)HfMe₂; (BzMe₄Cp)(3-CH₂—SiMe₃-Cp)HfMe₂;(Me₄Cp-CH₂—SiMe₃)(3-CH₂—SiMe₃-Cp)HfMe₂;(Me₄Cp-CH₂—SiMe₂Ph)(3-CH₂—SiMe₃-Cp)HfMe₂;(Me₄Cp-CH₂—SiMe₂Ph)(3-CH₂—SiMe₃-Cp)HfMe₂;(Me₄Cp-CH₂—SiMePh₂)(3-CH₂—SiMe₃-Cp)HfMe₂;(Me₄Cp-CH₂—SiPh₃)(3-CH₂—SiMe₃-Cp)HfMe₂;(Me₄Cp-CH₂—SiMe₂Cy)(3-CH₂—SiMe₃-Cp)HfMe₂;(Me₄Cp-CH₂—SiMeCy₂)(3-CH₂—SiMe₃-Cp)HfMe₂;(Me₄Cp-CH₂—SiCy₃)(3-CH₂—SiMe₃-Cp)HfMe₂; (EtMe₃Cp)(3-CH₂—SiMe₃-Cp)HfMe₂;(PrMe₃Cp)(3-CH₂—SiMe₃-Cp)HfMe₂; (BuMe₃Cp)(3-CH₂—SiMe₃-Cp)HfMe₂;(BzMe₃Cp)(3-CH₂—SiMe₃-Cp)HfMe₂; (Me₃Cp-CH₂—SiMe₃)(3-CH₂—SiMe₃-Cp)HfMe₂;(Me₃Cp-CH₂—SiMe₂Ph)(3-CH₂—SiPh₃-Cp)HfMe₂;(Me₃Cp-CH₂—SiMePh₂)(3-CH₂—SiMe₃-Cp)HfMe₂;(Me₃Cp-CH₂—SiPh₃)(3-CH₂—SiMe₃-Cp)HfMe₂;(Me₃Cp-CH₂—SiMe₂Cy)(3-CH₂—SiMe₃-Cp)HfMe₂;(Me₃Cp-CH₂—SiMeCy₂)(3-CH₂—SiMe₃-Cp)HfMe₂;(Me₃Cp-CH₂—SiCy₃)(3-CH₂—SiMe₃-Cp)HfMe₂; (MeEtCp)(3-CH₂—SiMe₃-Cp)HfMe₂;(MePrCp)(3-CH₂—SiMe₃-Cp)HfMe₂; MeBuCp)(3-CH₂—SiMe₃-Cp)HfMe₂;(BzMeCp)(3-CH₂—SiMe₃-Cp)HfMe₂; (EtPrCp)(3-CH₂—SiMe₃-Cp)HfMe₂;(EtBuCp)(3-CH₂—SiMe₃-Cp)HfMe₂; (BzEtCp)(3-CH₂—SiMe₃-Cp)HfMe₂;(PrBuCp)(3-CH₂—SiMe₃-Cp)HfMe₂; (BzPrCp)(3-CH₂—SiMe₃-Cp)HfMe₂;(BuBzCp)(3-CH₂—SiMe₃-Cp)HfMe₂; (Cp)(3-CH₂—SiMe₂Ph-Cp)HfMe₂;(MeCp)(3-CH₂—SiMe₂Ph-Cp)HfMe₂; (EtCp)(3-CH₂—SiMe₂Ph-Cp)HfMe₂;(PrCp)(3-CH₂—SiMe₂Ph-Cp)HfMe₂; (BuCp)(3-CH₂—SiMe₂Ph-Cp)HfMe₂;(BzCp)(3-CH₂—SiMe₂Ph-Cp)HfMe₂; (3-CH₂—SiMe₂Ph-Cp)₂HfMe₂;(Me₂Cp)(3-CH₂—SiMe₂Ph-Cp)HfMe₂; (Me₃Cp)(3-CH₂—SiMe₂Ph-Cp)HfMe₂;(Me₄Cp)(3-CH₂—SiMe₂Ph-Cp)HfMe₂; (Me₅Cp)(3-CH₂—SiMe₂Ph-Cp)HfMe₂;(Et₂Cp)(3-CH₂—SiMe₂Ph-Cp)HfMe₂; (Et₃Cp)(3-CH₂—SiMe₂Ph-Cp)HfMe₂;(Et₄Cp)(3-CH₂—SiMe₂Ph-Cp)HfMe₂; (Et₅Cp)(3-CH₂—SiMe₂Ph-Cp)HfMe₂;(Pr₂Cp)(3-CH₂—SiMe₂Ph-Cp)HfMe₂; (Pr₃Cp)(3-CH₂—SiMe₂Ph-Cp)HfMe₂;(Pr₄Cp)(3-CH₂—SiMe₂Ph-Cp)HfMe₂; (Pr₅Cp)(3-CH₂—SiMe₂Ph-Cp)HfMe₂;(Bu₂Cp)(3-CH₂—SiMe₂Ph-Cp)HfMe₂; (Bu₃Cp)(3-CH₂—SiMe₂Ph-Cp)HfMe₂;(Bu₄Cp)(3-CH₂—SiMe₂Ph-Cp)HfMe₂; (Bu₅Cp)(3-CH₂—SiMe₂Ph-Cp)HfMe₂;(Bz₂Cp)(3-CH₂—SiMe₂Ph-Cp)HfMe₂; (Bz₃Cp)(3-CH₂—SiMe₂Ph-Cp)HfMe₂;(Bz₄Cp)(3-CH₂—SiMe₂Ph-Cp)HfMe₂; (Bz₅Cp)(3-CH₂—SiMe₂Ph-Cp)HfMe₂;(EtMe₄Cp)(3-CH₂—SiMe₂Ph-Cp)HfMe₂; (PrMe₄Cp)(3-CH₂—SiMe₂Ph-Cp)HfMe₂;(BuMe₄Cp)(3-CH₂—SiMe₂Ph-Cp)HfMe₂; (BzMe₄Cp)(3-CH₂—SiMe₂Ph-Cp)HfMe₂;(Me₄Cp-CH₂—SiMe₃)(3-CH₂—SiMe₂Ph-Cp)HfMe₂;(Me₄Cp-CH₂—SiMe₂Ph)(3-CH₂—SiMe₂Ph-Cp)HfMe₂;(Me₄Cp-CH₂—SiMePh₂)(3-CH₂—SiMe₂Ph-Cp)HfMe₂;(Me₄Cp-CH₂—SiPh₃)(3-CH₂—SiMe₂Ph-Cp)HfMe₂;(Me₄Cp-CH₂—SiMe₂Cy)(3-CH₂—SiMe₂Ph-Cp)HfCl₂;(Me₄Cp-CH₂—SiMeCy₂)(3-CH₂—SiMe₂Ph-Cp)HfCl₂;(Me₄Cp-CH₂—SiCy₃)(3-CH₂—SiMe₂Ph-Cp)HfMe₂;(EtMe₃Cp)(3-CH₂—SiMe₂Ph-Cp)HfMe₂; (PrMe₃Cp)(3-CH₂—SiMe₂Ph-Cp)HfMe₂;(BuMe₃Cp)(3-CH₂—SiMe₂Ph-Cp)HfMe₂; (BzMe₃Cp)(3-CH₂—SiMe₂Ph-Cp)HfMe₂;(Me₃Cp-CH₂—SiMe₃)(3-CH₂—SiMe₂Ph-Cp)HfMe₂;(Me₃Cp-CH₂—SiMe₂Ph)(3-CH₂—SiMe₂Ph-Cp)HfMe₂;(Me₃Cp-CH₂—SiMePh₂)(3-CH₂—SiMe₂Ph-Cp)HfMe₂;(Me₃Cp-CH₂—SiPh₃)(3-CH₂—SiMe₂Ph-Cp)HfMe₂;(Me₃Cp-CH₂—SiMe₂Cy)(3-CH₂—SiMe₂Ph-Cp)HfMe₂;(Me₃Cp-CH₂—SiMeCy₂)(3-CH₂—SiMe₂Ph-Cp)HfMe₂;(Me₃Cp-CH₂—SiCy₃)(3-CH₂—SiMe₂Ph-Cp)HfMe₂;(MeEtCp)(3-CH₂—SiMe₂Ph-Cp)HfMe₂; (MePrCp)(3-CH₂—SiMe₂Ph-Cp)HfMe₂;(MeBuCp)(3-CH₂—SiMe₂Ph-Cp)HfMe₂; (BzMeCp)(3-CH₂—SiMe₂Ph-Cp)HfMe₂;(EtPrCp)(3-CH₂—SiMe₂Ph-Cp)HfMe₂; (EtBuCp)(3-CH₂—SiMe₂Ph-Cp)HfMe₂;(BzEtCp)(3-CH₂—SiMe₂Ph-Cp)HfMe₂; (PrBuCp)(3-CH₂—SiMe₂Ph-Cp)HfMe₂;(BzPrCp)(3-CH₂—SiMe₂Ph-Cp)HfMe₂; (BuBzCp)(3-CH₂—SiMe₂Ph-Cp)HfMe₂;(Cp)(3-CH₂—SiMePh₂-Cp)HfMe₂; (MeCp)(3-CH₂—SiMePh₂-Cp)HfMe₂;(EtCp)(3-CH₂—SiMePh₂-Cp)HfMe₂; (PrCp)(3-CH₂—SiMePh₂-Cp)HfMe₂;(BuCp)(3-CH₂—SiMePh₂-Cp)HfMe₂; ((BzCp)(3-CH₂—SiMePh₂-Cp)HfMe₂;(3-CH₂—SiMePh₂-Cp)₂HfMe₂; (Me₂Cp)(3-CH₂—SiMePh₂-Cp)HfMe₂;(Me₃Cp)(3-CH₂—SiMePh₂-Cp)HfMe₂; (Me₄Cp)(3-CH₂—SiMePh₂-Cp)HfMe₂;(Me₅Cp)(3-CH₂—SiMePh₂-Cp)HfMe₂; (Et₂Cp)(3-CH₂—SiMePh₂-Cp)HfMe₂;(Et₃Cp)(3-CH₂—SiMePh₂-Cp)HfMe₂; (Et₄Cp)(3-CH₂—SiMePh₂-Cp)HfMe₂;(Et₅Cp)(3-CH₂—SiMePh₂-Cp)HfMe₂; (Pr₂Cp)(3-CH₂—SiMePh₂-Cp)HfMe₂;(Pr₃Cp)(3-CH₂—SiMePh₂-Cp)HfMe₂; (Pr₄Cp)(3-CH₂—SiMePh₂-Cp)HfMe₂;(Pr₅Cp)(3-CH₂—SiMePh₂-Cp)HfMe₂; (Bu₂Cp)(3-CH₂—SiMePh₂-Cp)HfMe₂;(Bu₃Cp)(3-CH₂—SiMePh₂-Cp)HfMe₂; (Bu₄Cp)(3-CH₂—SiMePh₂-Cp)HfMe₂;(Bu₅Cp)(3-CH₂—SiMePh₂-Cp)HfMe₂; (Bz₂Cp)(3-CH₂—SiMePh₂-Cp)HfMe₂;(Bz₃Cp)(3-CH₂—SiMePh₂-Cp)HfMe₂; (Bz₄Cp)(3-CH₂—SiMePh₂-Cp)HfMe₂;(Bz₅Cp)(3-CH₂—SiMePh₂-Cp)HfMe₂; (EtMe₄Cp)(3-CH₂—SiMePh₂-Cp)HfMe₂;(PrMe₄Cp)(3-CH₂—SiMePh₂-Cp)HfMe₂; (BuMe₄Cp)(3-CH₂—SiMePh₂-Cp)HfMe₂;(PnMe₄Cp)(3-CH₂—SiMePh₂-Cp)HfMe₂; (HxMe₄Cp)(3-CH₂—SiMePh₂-Cp)HfMe₂;(BzMe₄Cp)(3-CH₂—SiMePh₂-Cp)HfMe₂;(Me₄Cp-CH₂—SiMe₃)(3-CH₂—SiMePh₂-Cp)HfMe₂;(Me₄Cp-CH₂—SiMe₂Ph)(3-CH₂—SiMePh₂-Cp)HfMe₂;(Me₄Cp-CH₂—SiMePh₂)(3-CH₂—SiMePh₂-Cp)HfMe₂;(Me₄Cp-CH₂—SiPh₃)(3-CH₂—SiMePh₂-Cp)HfMe₂;(Me₄Cp-CH₂—SiMe₂Cy)(3-CH₂—SiMePh₂-Cp)HfMe₂;(Me₄Cp-CH₂—SiMeCy₂)(3-CH₂—SiMePh₂-Cp)HfMe₂;(Me₄Cp-CH₂—SiCy₃)(3-CH₂—SiMePh₂-Cp)HfMe₂;(EtMe₃Cp)(3-CH₂—SiMePh₂-Cp)HfMe₂; (PrMe₃Cp)(3-CH₂—SiMePh₂-Cp)HfMe₂;(BuMe₃Cp)(3-CH₂—SiMePh₂-Cp)HfMe₂; (BzMe₃Cp)(3-CH₂—SiMePh₂-Cp)HfMe₂;(Me₃Cp-CH₂—SiMe₃)(3-CH₂—SiMePh₂-Cp)HfMe₂;(Me₃Cp-CH₂—SiMe₂Ph)(3-CH₂—SiMePh₂-Cp)HfMe₂;(Me₃Cp-CH₂—SiMePh₂)(3-CH₂—SiMePh₂-Cp)HfMe₂;(Me₃Cp-CH₂—SiPh₃)(3-CH₂—SiMePh₂-Cp)HfMe₂;(Me₃Cp-CH₂—SiMe₂Cy)(3-CH₂—SiMePh₂-Cp)HfMe₂;(Me₃Cp-CH₂—SiMeCy₂)(3-CH₂—SiMePh₂-Cp)HfMe₂;(Me₃Cp-CH₂—SiCy₃)(3-CH₂—SiMePh₂-Cp)HfMe₂;(MeEtCp)(3-CH₂—SiMePh₂-Cp)HfMe₂; (MePrCp)(3-CH₂—SiMePh₂-Cp)HfMe₂;(MeBuCp)(3-CH₂—SiMePh₂-Cp)HfMe₂; (BzMeCp)(3-CH₂—SiMePh₂-Cp)HfMe₂;(EtPrCp)(3-CH₂—SiMePh₂-Cp)HfMe₂; (EtBuCp)(3-CH₂—SiMePh₂-Cp)HfMe₂;(BzEtCp)(3-CH₂—SiMePh₂-Cp)HfMe₂; (PrBuCp)(3-CH₂—SiMePh₂-Cp)HfMe₂;(BzPrCp)(3-CH₂—SiMePh₂-Cp)HfMe₂; (BuBzCp)(3-CH₂—SiMePh₂-Cp)HfMe₂;(Cp)(3-CH₂—SiPh₃-Cp)HfMe₂; (MeCp)(3-CH₂—SiPh₃-Cp)HfMe₂;(EtCp)(3-CH₂—SiPh₃-Cp)HfMe₂; (PrCp)(3-CH₂—SiPh₃-Cp)HfMe₂;(BuCp)(3-CH₂—SiPh₃-Cp)HfMe₂; (BzCp)(3-CH₂—SiPh₃-Cp)HfMe₂;(3-CH₂—SiPh₃-Cp)₂HfMe₂; (Me₂Cp)(3-CH₂—SiPh₃-Cp)HfMe₂;(Me₃Cp)(3-CH₂—SiPh₃-Cp)HfMe₂; (Me₄Cp)(3-CH₂—SiPh₃-Cp)HfMe₂;(Me₅Cp)(3-CH₂—SiPh₃-Cp)HfMe₂; (Et₂Cp)(3-CH₂—SiPh₃-Cp)HfMe₂;(Et₃Cp)(3-CH₂—SiPh₃-Cp)HfMe₂; (Et₄Cp)(3-CH₂—SiPh₃-Cp)HfMe₂;(Et₅Cp)(3-CH₂—SiPh₃-Cp)HfMe₂; (Pr₂Cp)(3-CH₂—SiPh₃-Cp)HfMe₂;(Pr₃Cp)(3-CH₂—SiPh₃-Cp)HfMe₂; (Pr₄Cp)(3-CH₂—SiPh₃-Cp)HfMe₂;(Pr₅Cp)(3-CH₂—SiPh₃-Cp)HfMe₂; (Bu₂Cp)(3-CH₂—SiPh₃-Cp)HfMe₂;(Bu₃Cp)(3-CH₂—SiPh₃-Cp)HfMe₂; (Bu₄Cp)(3-CH₂—SiPh₃-Cp)HfMe₂;(Bu₅Cp)(3-CH₂—SiPh₃-Cp)HfMe₂; (Bz₂Cp)(3-CH₂—SiPh₃-Cp)HfMe₂;(Bz₃Cp)(3-CH₂—SiPh₃-Cp)HfMe₂; (Bz₄Cp)(3-CH₂—SiPh₃-Cp)HfMe₂;(Bz₅Cp)(3-CH₂—SiPh₃-Cp)HfMe₂; (EtMe₄Cp)(3-CH₂—SiPh₃-Cp)HfMe₂;(PrMe₄Cp)(3-CH₂—SiPh₃-Cp)HfMe₂; (BuMe₄Cp)(3-CH₂—SiPh₃-Cp)HfMe₂;(BzMe₄Cp)(3-CH₂—SiPh₃-Cp)HfMe₂; (Me₄Cp-CH₂—SiMe₃)(3-CH₂—SiPh₃-Cp)HfMe₂;(Me₄Cp-CH₂—SiMe₂Ph)(3-CH₂—SiPh₃-Cp)HfMe₂;(Me₄Cp-CH₂—SiMePh₂)(3-CH₂—SiPh₃-Cp)HfMe₂;(Me₄Cp-CH₂—SiPh₃)(3-CH₂—SiPh₃-Cp)HfMe₂;(Me₄Cp-CH₂—SiMe₂Cy)(3-CH₂—SiPh₃-Cp)HfMe₂;(Me₄Cp-CH₂—SiMeCy₂)(3-CH₂—SiPh₃-Cp)HfMe₂;(Me₄Cp-CH₂—SiCy₃)(3-CH₂—SiPh₃-Cp)HfMe₂; (EtMe₃Cp)(3-CH₂—SiPh₃-Cp)HfMe₂;(PrMe₃Cp)(3-CH₂—SiPh₃-Cp)HfMe₂; (BuMe₃Cp)(3-CH₂—SiPh₃-Cp)HfMe₂;(BzMe₃Cp)(3-CH₂—SiPh₃-Cp)HfMe₂; (Me₃Cp-CH₂—SiMe₃)(3-CH₂—SiPh₃-Cp)HfMe₂;(Me₃Cp-CH₂—SiMe₂Ph)(3-CH₂—SiPh₃-Cp)HfMe₂;(Me₃Cp-CH₂—SiMePh₂)(3-CH₂—SiPh₃-Cp)HfMe₂;(Me₃Cp-CH₂—SiPh₃)(3-CH₂—SiPh₃-Cp)HfMe₂;(Me₃Cp-CH₂—SiMe₂Cy)(3-CH₂—SiPh₃-Cp)HfMe₂;(Me₃Cp-CH₂—SiMeCy₂)(3-CH₂—SiPh₃-Cp)HfMe₂;(Me₃Cp-CH₂—SiCy₃)(3-CH₂—SiPh₃-Cp)HfMe₂; (MeEtCp)(3-CH₂—SiPh₃-Cp)HfMe₂;(MePrCp)(3-CH₂—SiPh₃-Cp)HfMe₂; (MeBuCp)(3-CH₂—SiPh₃-Cp)HfMe₂;(BzMeCp)(3-CH₂—SiPh₃-Cp)HfMe₂; (EtPrCp)(3-CH₂—SiPh₃-Cp)HfMe₂;(EtBuCp)(3-CH₂—SiPh₃-Cp)HfMe₂; (BzEtCp)(3-CH₂—SiPh₃-Cp)HfMe₂;(PrBuCp)(3-CH₂—SiPh₃-Cp)HfMe₂; (BzPrCp)(3-CH₂—SiPh₃-Cp)HfMe₂;(BuBzCp)(3-CH₂—SiPh₃-Cp)HfMe₂; (Cp)(3-CH₂—SiCyMe₂-Cp)HfMe₂;(MeCp)(3-CH₂—SiCyMe₂-Cp)HfMe₂; (EtCp)(3-CH₂—SiCyMe₂-Cp)HfMe₂;(PrCp)(3-CH₂—SiCyMe₂-Cp)HfMe₂; (BuCp)(3-CH₂—SiCyMe₂-Cp)HfMe₂;(BzCp)(3-CH₂—SiCyMe₂-Cp)HfMe₂; (3-CH₂—SiCyMe₂-Cp)₂HfMe₂;(Me₂Cp)(3-CH₂—SiCyMe₂-Cp)HfMe₂; (Me₃Cp)(3-CH₂—SiCyMe₂-Cp)HfMe₂;(Me₄Cp)(3-CH₂—SiCyMe₂-Cp)HfMe₂; (Me₅Cp)(3-CH₂—SiCyMe₂-Cp)HfMe₂;(Et₂Cp)(3-CH₂—SiCyMe₂-Cp)HfMe₂; (Et₃Cp)(3-CH₂—SiCyMe₂-Cp)HfMe₂;(Et₄Cp)(3-CH₂—SiCyMe₂-Cp)HfMe₂; (Et₅Cp)(3-CH₂—SiCyMe₂-Cp)HfMe₂;(Pr₂Cp)(3-CH₂—SiCyMe₂-Cp)HfMe₂; (Pr₃Cp)(3-CH₂—SiCyMe₂-Cp)HfMe₂;(Pr₄Cp)(3-CH₂—SiCyMe₂-Cp)HfMe₂; (Pr₅Cp)(3-CH₂—SiCyMe₂-Cp)HfMe₂;(Bu₂Cp)(3-CH₂—SiCyMe₂-Cp)HfMe₂; (Bu₃Cp)(3-CH₂—SiCyMe₂-Cp)HfMe₂;(Bu₄Cp)(3-CH₂—SiCyMe₂-Cp)HfMe₂; (Bu₅Cp)(3-CH₂—SiCyMe₂-Cp)HfMe₂;(Bz₂Cp)(3-CH₂—SiCyMe₂-Cp)HfMe₂; (Bz₃Cp)(3-CH₂—SiCyMe₂-Cp)HfMe₂;(Bz₄Cp)(3-CH₂—SiCyMe₂-Cp)HfMe₂; (Bz₅Cp)(3-CH₂—SiCyMe₂-Cp)HfMe₂;(EtMe₄Cp)(3-CH₂—SiCyMe₂-Cp)HfMe₂; (PrMe₄Cp)(3-CH₂—SiCyMe₂-Cp)HfMe₂;(BuMe₄Cp)(3-CH₂—SiCyMe₂-Cp)HfMe₂; (BzMe₄Cp)(3-CH₂—SiCyMe₂-Cp)HfMe₂;(Me₄Cp-CH₂—SiMe₃)(3-CH₂—SiCyMe₂-Cp)HfMe₂;(Me₄Cp-CH₂—SiCyMe₂Ph)(3-CH₂—SiCyMe₂-Cp)HfMe₂;(Me₄Cp-CH₂—SiMePh₂)(3-CH₂—SiCyMe₂-Cp)HfMe₂;(Me₄Cp-CH₂—SiPh₃)(3-CH₂—SiCyMe₂-Cp)HfMe₂;(Me₄Cp-CH₂—SiMe₂Cy)(3-CH₂—SiCyMe₂-Cp)HfMe₂;(Me₄Cp-CH₂—SiMeCy₂)(3-CH₂—SiCyMe₂-Cp)HfMe₂;(Me₄Cp-CH₂—SiCy₃)(3-CH₂—SiCyMe₂-Cp)HfMe₂;(EtMe₃Cp)(3-CH₂—SiCyMe₂-Cp)HfMe₂; (PrMe₃Cp)(3-CH₂—SiCyMe₂-Cp)HfMe₂;(BuMe₃Cp)(3-CH₂—SiCyMe₂-Cp)HfMe₂; (BzMe₃Cp)(3-CH₂—SiCyMe₂-Cp)HfMe₂;(Me₃Cp-CH₂—SiMe₃)(3-CH₂—SiCyMe₂-Cp)HfMe₂;(Me₃Cp-CH₂—SiMe₂Ph)(3-CH₂—SiCyMe₂-Cp)HfMe₂;(Me₃Cp-CH₂—SiMePh₂)(3-CH₂—SiCyMe₂-Cp)HfMe₂;(Me₃Cp-CH₂—SiPh₃)(3-CH₂—SiCyMe₂-Cp)HfMe₂;(Me₃Cp-CH₂—SiMe₂Cy)(3-CH₂—SiCyMe₂-Cp)HfMe₂;(Me₃Cp-CH₂—SiMeCy₂)(3-CH₂—SiCyMe₂-Cp)HfMe₂;(Me₃Cp-CH₂—SiCy₃)(3-CH₂—SiCyMe₂-Cp)HfMe₂;(MeEtCp)(3-CH₂—SiCyMe₂-Cp)HfMe₂; (MePrCp)(3-CH₂—SiCyMe₂-Cp)HfMe₂;(MeBuCp)(3-CH₂—SiCyMe₂-Cp)HfMe₂; (BzMeCp)(3-CH₂—SiCyMe₂-Cp)HfMe₂;(EtPrCp)(3-CH₂—SiCyMe₂-Cp)HfMe₂; (EtBuCp)(3-CH₂—SiCyMe₂-Cp)HfMe₂;(BzEtCp)(3-CH₂—SiCyMe₂-Cp)HfMe₂; (PrBuCp)(3-CH₂—SiCyMe₂-Cp)HfMe₂;(BzPrCp)(3-CH₂—SiCyMe₂-Cp)HfMe₂; (BuBzCp)(3-CH₂—SiCyMe₂-Cp)HfMe₂;(Cp)(3-CH₂—SiCy₂Me-Cp)HfMe₂; (MeCp)(3-CH₂—SiCy₂Me-Cp)HfMe₂;(EtCp)(3-CH₂—SiCy₂Me-Cp)HfMe₂; (PrCp)(3-CH₂—SiCy₂Me-Cp)HfMe₂;(BuCp)(3-CH₂—SiCy₂Me-Cp)HfMe₂; (BzCp)(3-CH₂—SiCy₂Me-Cp)HfMe₂;(3-CH₂—SiCy₂Me-Cp)₂HfMe₂; (Me₂Cp)(3-CH₂—SiCy₂Me-Cp)HfMe₂;(Me₃Cp)(3-CH₂—SiCy₂Me-Cp)HfMe₂; (Me₄Cp)(3-CH₂—SiCy₂Me-Cp)HfMe₂;(Me₅Cp)(3-CH₂—SiCy₂Me-Cp)HfMe₂; (Et₂Cp)(3-CH₂—SiCy₂Me-Cp)HfMe₂;(Et₃Cp)(3-CH₂—SiCy₂Me-Cp)HfMe₂; (Et₄Cp)(3-CH₂—SiCy₂Me-Cp)HfMe₂;(Et₅Cp)(3-CH₂—SiCy₂Me-Cp)HfMe₂; (Pr₂Cp)(3-CH₂—SiCy₂Me-Cp)HfMe₂;(Pr₃Cp)(3-CH₂—SiCy₂Me-Cp)HfMe₂; (Pr₄Cp)(3-CH₂—SiCy₂Me-Cp)HfMe₂;(Pr₅Cp)(3-CH₂—SiCy₂Me-Cp)HfMe₂; (Bu₂Cp)(3-CH₂—SiCy₂Me-Cp)HfMe₂;(Bu₃Cp)(3-CH₂—SiCy₂Me-Cp)HfCl₂; (Bu₄Cp)(3-CH₂—SiCy₂Me-Cp)HfCl₂;(Bu₅Cp)(3-CH₂—SiCy₂Me-Cp)HfCl₂; (Bz₂Cp)(3-CH₂—SiCy₂Me-Cp)HfMe₂;(Bz₃Cp)(3-CH₂—SiCy₂Me-Cp)HfMe₂; (Bz₄Cp)(3-CH₂—SiCy₂Me-Cp)HfCl₂;(Bz₅Cp)(3-CH₂—SiCy₂Me-Cp)HfCl₂; (EtMe₄Cp)(3-CH₂—SiCy₂Me-Cp)HfCl₂;(PrMe₄Cp)(3-CH₂—SiCy₂Me-Cp)HfMe₂; (BuMe₄Cp)(3-CH₂—SiCy₂Me-Cp)HfMe₂;(BzMe₄Cp)(3-CH₂—SiCy₂Me-Cp)HfMe₂;(Me₄Cp-CH₂—SiMe₃)(3-CH₂—SiCy₂Me-Cp)HfMe₂;(Me₄Cp-CH₂—SiMe₂Ph)(3-CH₂—SiCy₂Me-Cp)HfMe₂;(Me₄Cp-CH₂—SiMePh₂)(3-CH₂—SiCy₂Me-Cp)HfMe₂;(Me₄Cp-CH₂—SiPh₃)(3-CH₂—SiCy₂Me-Cp)HfMe₂;(Me₄Cp-CH₂—SiMe₂Cy)(3-CH₂—SiCy₂Me-Cp)HfMe₂;(Me₄Cp-CH₂—SiMeCy₂)(3-CH₂—SiCy₂Me-Cp)HfMe₂;(Me₄Cp-CH₂—SiCy₃)(3-CH₂-Cy₂Me-Cp)HfMe₂;(EtMe₃Cp)(3-CH₂—SiCy₂Me-Cp)HfMe₂; (PrMe₃Cp)(3-CH₂—SiCy₂Me-Cp)HfMe₂;(BuMe₃Cp)(3-CH₂—SiCy₂Me-Cp)HfMe₂; (BzMe₃Cp)(3-CH₂—SiCy₂Me-Cp)HfMe₂;(Me₃Cp-CH₂—SiMe₃)(3-CH₂—SiCy₂Me-Cp)HfMe₂;(Me₃Cp-CH₂—SiMe₂Ph)(3-CH₂—SiCy₂Me-Cp)HfMe₂;(Me₃Cp-CH₂—SiMePh₂)(3-CH₂—SiCy₂Me-Cp)HfMe₂;(Me₃Cp-CH₂—SiPh₃)(3-CH₂—SiCy₂Me-Cp)HfMe₂;(Me₃Cp-CH₂—SiMe₂Cy)(3-CH₂—SiCy₂Me-Cp)HfMe₂;(Me₃Cp-CH₂—SiMeCy₂)(3-CH₂—SiCy₂Me-Cp)HfMe₂;(Me₃Cp-CH₂—SiCy₃)(3-CH₂—SiCy₂Me-Cp)HfMe₂;(MeEtCp)(3-CH₂—SiCy₂Me-Cp)HfMe₂; (MePrCp)(3-CH₂—SiCy₂Me-Cp)HfMe₂;(MeBuCp)(3-CH₂—SiCy₂Me-Cp)HfMe₂; (BzMeCp)(3-CH₂—SiCy₂Me-Cp)HfMe₂;(EtPrCp)(3-CH₂—SiCy₂Me-Cp)HfMe₂; (EtBuCp)(3-CH₂—SiCy₂Me-Cp)HfMe₂;(BzEtCp)(3-CH₂—SiCy₂Me-Cp)HfMe₂; (PrBuCp)(3-CH₂—SiCy₂Me-Cp)HfMe₂;(BzPrCp)(3-CH₂—SiCy₂Me-Cp)HfMe₂; (BuBzCp)(3-CH₂—SiCy₂Me-Cp)HfMe₂;(Cp)(3-CH₂—SiCy₃-Cp)HfMe₂; (MeCp)(3-CH₂—SiCy₃-Cp)HfMe₂;(EtCp)(3-CH₂—SiCy₃-Cp)HfMe₂; (PrCp)(3-CH₂—SiCy₃-Cp)HfMe₂;(BuCp)(3-CH₂—SiCy₃-Cp)HfMe₂ (BzCp)(3-CH₂—SiCy₃-Cp)HfMe₂;(3-CH₂—SiCy₃-Cp)₂HfMe₂; (Me₂Cp)(3-CH₂—SiCy₃-Cp)HfMe₂;(Me₃Cp)(3-CH₂—SiCy₃-Cp)HfMe₂; (Me₄Cp)(3-CH₂—SiCy₃-Cp)HfMe₂;(Me₅Cp)(3-CH₂—SiCy₃-Cp)HfMe₂; (Et₂Cp)(3-CH₂—SiCy₃-Cp)HfMe₂;(Et₃Cp)(3-CH₂—SiCy₃-Cp)HfMe₂; (Et₄Cp)(3-CH₂—SiCy₃-Cp)HfMe₂;(Et₅Cp)(3-CH₂—SiCy₃-Cp)HfMe₂; (Pr₂Cp)(3-CH₂—SiCy₃-Cp)HfMe₂;(Pr₃Cp)(3-CH₂—SiCy₃-Cp)HfMe₂; (Pr₄Cp)(3-CH₂—SiCy₃-Cp)HfMe₂;(Pr₅Cp)(3-CH₂—SiCy₃-Cp)HfMe₂; (Bu₂Cp)(3-CH₂—SiCy₃-Cp)HfMe₂;(Bu₃Cp)(3-CH₂—SiCy₃-Cp)HfMe₂; (Bu₄Cp)(3-CH₂—SiCy₃-Cp)HfMe₂;(Bu₅Cp)(3-CH₂—SiCy₃-Cp)HfMe₂; (Bz₂Cp)(3-CH₂—SiCy₃-Cp)HfMe₂;(Bz₃Cp)(3-CH₂—SiCy₃-Cp)HfMe₂; (Bz₄Cp)(3-CH₂—SiCy₃-Cp)HfMe₂;(Bz₅Cp)(3-CH₂—SiCy₃-Cp)HfMe₂; (EtMe₄Cp)(3-CH₂—SiCy₃-Cp)HfMe₂;(PrMe₄Cp)(3-CH₂—SiCy₃-Cp)HfMe₂; (BuMe₄Cp)(3-CH₂—SiCy₃-Cp)HfMe₂;(BzMe₄Cp)(3-CH₂—SiCy₃-Cp)HfMe₂; (Me₄Cp-CH₂—SiMe₃)(3-CH₂—SiCy₃-Cp)HfMe₂;(Me₄Cp-CH₂—SiMe₂Ph)(3-CH₂—SiCy₃-Cp)HfMe₂;(Me₄Cp-CH₂—SiMePh₂)(3-CH₂—SiCy₃-Cp)HfMe₂;(Me₄Cp-CH₂—SiPh₃)(3-CH₂—SiCy₃-Cp)HfMe₂;(Me₄Cp-CH₂—SiMe₂Cy)(3-CH₂—SiCy₃-Cp)HfMe₂;(Me₄Cp-CH₂—SiMeCy₂)(3-CH₂—SiCy₃-Cp)HfMe₂;(Me₄Cp-CH₂—SiCy₃)(3-CH₂—SiCy₃-Cp)HfMe₂; (EtMe₃Cp)(3-CH₂—SiCy₃-Cp)HfMe₂;(PrMe₃Cp)(3-CH₂—SiCy₃-Cp)HfMe₂; (BuMe₃Cp)(3-CH₂—SiCy₃-Cp)HfMe₂;(BzMe₃Cp)(3-CH₂—SiCy₃-Cp)HfMe₂; (Me₃Cp-CH₂—SiMe₃)(3-CH₂—SiCy₃-Cp)HfMe₂;(Me₃Cp-CH₂—SiMe₂Ph)(3-CH₂—SiCy₃-Cp)HfMe₂;(Me₃Cp-CH₂—SiMePh₂)(3-CH₂—SiCy₃-Cp)HfMe₂;(Me₃Cp-CH₂—SiPh₃)(3-CH₂—SiCy₃-Cp)HfMe₂;(Me₃Cp-CH₂—SiMe₂Cy)(3-CH₂—SiCy₃-Cp)HfMe₂;(Me₃Cp-CH₂—SiMeCy₂)(3-CH₂—SiCy₃-Cp)HfMe₂;(Me₃Cp-CH₂—SiCy₃)(3-CH₂—SiCy₃-Cp)HfMe₂; (MeEtCp)(3-CH₂—SiCy₃-Cp)HfMe₂;(MePrCp)(3-CH₂—SiCy₃-Cp)HfMe₂; (MeBuCp)(3-CH₂—SiCy₃-Cp)HfMe₂;(BzMeCp)(3-CH₂—SiCy₃-Cp)HfMe₂; (EtPrCp)(3-CH₂—SiPCy-Cp)HfMe₂;(EtBuCp)(3-CH₂—SiCy₃-Cp)HfMe₂; (BzEtCp)(3-CH₂—SiCy₃-Cp)HfMe₂;(PrBuCp)(3-CH₂—SiCy₃-Cp)HfMe₂; (BzPrCp)(3-CH₂—SiCy₃-Cp)HfMe₂;(BuBzCp)(3-CH₂—SiCy₃-Cp)HfMe₂; (2-Me, 3-CH₂—SiMe₃-Ind)₂HfMe₂; (2-Et,3-CH₂—SiMe₃-Ind)₂HfMe₂; (2-Pr, 3-CH₂—SiMe₃-Ind)₂HfMe₂; (2-Bu,3-CH₂—SiMe₃-Ind)₂HfMe₂; (2-Ph, 3-CH₂—SiMe₃-Ind)₂HfMe₂; (2-Bz,3-CH₂—SiMe₃-Ind)₂HfMe₂; (2-Me, 3-CH₂—SiMe₂Ph-Ind)₂HfMe₂; (2-Et,3-CH₂—SiMe₂Ph-Ind)₂HfMe₂; (2-Pr, 3-CH₂—SiMe₂Ph-Ind)₂HfMe₂; (2-Bu,3-CH₂—SiMe₂Ph-Ind)₂HfMe₂; (2-Ph, 3-CH₂—SiMe₂Ph-Ind)₂HfMe₂; (2-Bz,3-CH₂—SiMe₂Ph-Ind)₂HfMe₂; (2-Me, 3-CH₂—SiMePh₂-Ind)₂HfMe₂; (2-Et,3-CH₂—SiMePh₂-Ind)₂HfMe₂; (2-Pr, 3-CH₂—SiMePh₂-Ind)₂HfMe₂; (2-Bu,3-CH₂—SiMePh₂-Ind)₂HfMe₂; (2-Ph, 3-CH₂—SiMePh₂-Ind)₂HfMe₂; (2-Bz,3-CH₂—SiMePh₂-Ind)₂HfMe₂; (2-Me, 3-CH₂—SiPh₃-Ind)₂HfMe₂; (2-Et,3-CH₂—SiPh₃-Ind)₂HfMe₂; (2-Pr, 3-CH₂—SiPh₃-Ind)₂HfMe₂; (2-Bu,3-CH₂—SiPh₃-Ind)₂HfMe₂; (2-Ph, 3-CH₂—SiPh₃-Ind)₂HfMe₂; (2-Bz,3-CH₂—SiPh₃-Ind)₂HfMe₂; (2-Me, 3-CH₂—SiCyMe₂-Ind)₂HfMe₂; (2-Et,3-CH₂—SiCyMe₂-Ind)₂HfMe₂; (2-Pr, 3-CH₂—SiCyMe₂-Ind)₂HfMe₂; (2-Bu,3-CH₂—SiCyMe₂-Ind)₂HfMe₂; (2-Ph, 3-CH₂—SiCyMe₂-Ind)₂HfMe₂; (2-Bz,3-CH₂—SiCyMe₂-Ind)₂HfMe₂; (2-Me, 3-CH₂—SiCy₂Me-Ind)₂HfMe₂; (2-Et,3-CH₂—SiCy₂Me-Ind)₂HfMe₂; (2-Pr, 3-CH₂—SiCy₂Me-Ind)₂HfMe₂; (2-Bu,3-CH₂—SiCy₂Me-Ind)₂HfMe₂; (2-Ph, 3-CH₂—SiCy₂Me-Ind)₂HfMe₂; (2-Bz,3-CH₂—SiCy₂Me-Ind)₂HfMe₂; (2-Me, 3-CH₂—SiCy₃-Ind)₂HfMe₂; (2-Et,3-CH₂—SiCy₃-Ind)₂HfMe₂; (2-Pr, 3-CH₂—SiCy₃-Ind)₂HfMe₂; (2-Bu,3-CH₂—SiCy₃-Ind)₂HfMe₂; (2-Ph, 3-CH₂—SiCy₃-Ind)₂HfMe₂; (2-Bz,3-CH₂—SiCy₃-Ind)₂HfMe₂; (2-Me, 3-CH₂—SiMe₃-Ind)(3-CH₂—SiMe₃-Cp)HfMe₂;(2-Et, 3-CH₂— SiMe₃-Ind) (3-CH₂—SiMe₃-Cp)HfMe₂; (2-Pr,3-CH₂—SiMe₃-Ind)(3-CH₂—SiMe₃-Cp)HfMe₂; (2-Bu,3-CH₂—SiMe₃-Ind)(3-CH₂—SiMe₃-Cp)HfMe₂; (2-Pn,3-CH₂—SiMe₃-Ind)(3-CH₂—SiMe₃-Cp)HfMe₂; (2-Hx,3-CH₂—SiMe₃-Ind)(3-CH₂—SiMe₃-Cp)HfMe₂; (2-Ph,3-CH₂—SiMe₃-Ind)(3-CH₂—SiMe₃-Cp)HfMe₂; (2-Me,3-CH₂—SiMe₂Ph-Ind)(3-CH₂—SiMe₃-Cp)HfMe₂; (2-Et,3-CH₂—SiMe₂Ph-Ind)(3-CH₂—SiMe₃-Cp)HfMe₂; (2-Pr,3-CH₂—SiMe₂Ph-Ind)(3-CH₂—SiMe₃-Cp)HfMe₂; (2-Bu,3-CH₂—SiMe₂Ph-Ind)(3-CH₂—SiMe₃-Cp)HfMe₂; (2-Pn,3-CH₂—SiMe₂Ph-Ind)(3-CH₂—SiMe₂Ph-Cp)HfMe₂; (2-Hx,3-CH₂—SiMe₂Ph-Ind)(3-CH₂—SiMe₃-Cp)HfMe₂; (2-Ph,3-CH₂—SiMe₂Ph-Ind)(3-CH₂—SiMe₃-Cp)HfMe₂; (2-Me,3-CH₂—SiMePh₂-Ind)(3-CH₂—SiMe₃-Cp)HfMe₂; (2-Et,3-CH₂—SiMePh₂-Ind)(3-CH₂—SiMe₃-Cp)HfMe₂; (2-Pr,3-CH₂—SiMePh₂-Ind)(3-CH₂—SiMe₃-Cp)HfMe₂; (2-Bu,3-CH₂—SiMePh₂-Ind)(3-CH₂—SiMe₃-Cp)HfMe₂; (2-Pn,3-CH₂—SiMePh₂-Ind)(3-CH₂—SiMe₂Ph-Cp)HfMe₂; (2-Hx,3-CH₂—SiMePh₂-Ind)(3-CH₂—SiMe₃-Cp)HfMe₂; (2-Ph,3-CH₂—SiMePh₂-Ind)(3-CH₂—SiMe₃-Cp)HfMe₂; (2-Me,3-CH₂—SiPh₃-Ind)(3-CH₂—SiMe₃-Cp)HfMe₂; (2-Et,3-CH₂—SiPh₃-Ind)(3-CH₂—SiMe₃-Cp)HfMe₂; (2-Pr,3-CH₂—SiPh₃-Ind)(3-CH₂—SiMe₃-Cp)HfMe₂; (2-Bu,3-CH₂—SiPh₃-Ind)(3-CH₂—SiMe₃-Cp)HfMe₂; (2-Pn,3-CH₂—SiPh₃-Ind)(3-CH₂—SiMe₂Ph-Cp)HfMe₂; (2-Hx,3-CH₂—SiPh₃-Ind)(3-CH₂—SiMe₃-Cp)HfMe₂; (2-Ph, 3-CH₂—SiPh₃-Ind)(3-CH₂—SiMe₃-Cp)HfMe₂; (2-Me,3-CH₂—SiCyMe₂-Ind)(3-CH₂—SiMe₃-Cp)HfMe₂; (2-Et,3-CH₂—SiCyMe₂-Ind)(3-CH₂—SiMe₃-Cp)HfMe₂; (2-Pr,3-CH₂—SiCyMe₂-Ind)(3-CH₂—SiMe₃-Cp)HfMe₂; (2-Bu,3-CH₂—SiCyMe₂-Ind)(3-CH₂—SiMe₃-Cp)HfMe₂; (2-Pn,3-CH₂—SiCyMe₂-Ind)(3-CH₂—SiMe₂Ph-Cp)HfMe₂; (2-Hx,3-CH₂—SiCyMe₂-Ind)(3-CH₂—SiMe₃-Cp)HfMe₂; (2-Ph,3-CH₂—SiCyMe₂-Ind)(3-CH₂—SiMe₃-Cp)HfMe₂, and the alkyl or halideversions thereof where the Me₂ is replaced with Bz₂, Et₂, Ph₂, Cl₂, Br₂or I₂.

The Second Unbridged Metallocene

Unbridged zirconium metallocenes useful herein are further representedby the formula (C):Cp_(m)ZrX′_(q)  (C)wherein each Cp is independently a cyclopentadienyl group (such ascyclopentadiene, indene or fluorene) which may be substituted orunsubstituted, X′ is a leaving group (such as a halide, a hydride, analkyl group, an alkenyl group or an arylalkyl group), and m=1 or 2, n=0,1, 2 or 3, q=0, 1, 2, or 3, and the sum of m+q is equal to the oxidationstate of the transition metal, preferably 3 or 4, preferably 4. In someembodiments, m is 2.

In an embodiment each X′ may be independently a halide, a hydride, analkyl group, an alkenyl group or an arylalkyl group.

Alternatively, each X′ is independently selected from the groupconsisting of hydrocarbyl radicals having from 1 to 20 carbon atoms,aryls, hydrides, amides, alkoxides, sulfides, phosphides, halides,dienes, amines, phosphines, ethers, and a combination thereof, (two X'smay form a part of a fused ring or a ring system), preferably each X′ isindependently selected from halides, aryls and C₁ to C₅ alkyl groups,preferably each X′ is a phenyl, methyl, ethyl, propyl, butyl, pentyl, orchloro group.

Typically, each Cp is independently a substituted or unsubstitutedcyclopentadiene, a substituted or unsubstituted indene, or a substitutedor unsubstituted fluorene.

Independently, each Cp may be substituted with a combination ofsubstituent groups R.

Non-limiting examples of substituent groups R include one or more fromthe group selected from hydrogen, or linear, branched alkyl radicals, oralkenyl radicals, alkynyl radicals, cycloalkyl radicals or arylradicals, acyl radicals, alkoxy radicals, aryloxy radicals, alkylthioradicals, dialkylamino radicals, alkoxycarbonyl radicals,aryloxycarbonyl radicals, carbamoyl radicals, alkyl- ordialkyl-carbamoyl radicals, acyloxy radicals, acylamino radicals,aroylamino radicals, straight, branched or cyclic, alkylene radicals, orcombination thereof. In a preferred embodiment, substituent groups Rhave up to 50 non-hydrogen atoms, preferably from 1 to 30 carbon, thatcan also be substituted with halogens or heteroatoms or the like.Non-limiting examples of alkyl substituents R include methyl, ethyl,propyl, butyl, pentyl, hexyl, cyclopentyl, cyclohexyl, benzyl or phenylgroups and the like, including all their isomers, for example, tertiarybutyl, isopropyl and the like. Other hydrocarbyl radicals includefluoromethyl, fluoroethyl, difluoroethyl, iodopropyl, bromohexylchlorobenzyl, and hydrocarbyl substituted organometalloid radicalsincluding trimethylsilyl, trimethylgermyl, methyldiethylsilyl and thelike; and halocarbyl-substituted organometalloid radicals includingtris(trifluoromethyl)-silyl, methylbis(difluoromethyl)silyl,bromomethyldimethylgermyl and the like; and disubstituted boron radicalsincluding dimethylboron for example; and disubstituted pnictogenradicals including dimethylamine, dimethylphosphine, diphenylamine,methylphenylphosphine, chalcogen radicals including methoxy, ethoxy,propoxy, phenoxy, methylsulfide, and ethylsulfide. Non-hydrogensubstituents R include the atoms carbon, silicon, boron, aluminum,nitrogen, phosphorus, oxygen, tin, sulfur, germanium and the like,including olefins such as, but not limited to, olefinically unsaturatedsubstituents including vinyl-terminated ligands, for example but-3-enyl,prop-2-enyl, hex-5-enyl, and the like. Also, at least two R groups,preferably two adjacent R groups, may be joined to form a ring structurehaving from 3 to 30 atoms selected from carbon, nitrogen, oxygen,phosphorus, silicon, germanium, aluminum, boron, or a combinationthereof.

In an embodiment of Cp, the substituent(s) R are independentlyhydrocarbyl groups, heteroatoms, or heteroatom containing groups, suchas methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl,decyl, undecyl, dodecyl or an isomer thereof, N, O, S, P, or a C₁ to C₂₀hydrocarbyl substituted with an N, O, S or P heteroatom or heteroatomcontaining group (typically having up to 12 atoms, including the N, O,S, and P heteroatoms).

Non-limiting examples of Cp include (substituted or unsubstituted)cyclopentadienyl, cyclopentaphenanthreneyl, indenyl, benzindenyl,fluorenyl, octahydrofluorenyl, cyclooctatetraenyl,cyclopentacyclododecene, azenyl, azulene, pentalene, phosphoyl,phosphinimine (WO 99/40125), pyrrolyl, pyrazolyl, carbazolyl,borabenzene, and the like, including hydrogenated versions thereof, forexample tetrahydroindenyl. In another embodiment, each Cp may,independently comprise one or more heteroatoms, for example, nitrogen,silicon, boron, germanium, sulfur, and phosphorus, in combination withcarbon atoms to form an open, acyclic, or preferably a fused, ring orring system, for example, a heterocyclopentadienyl ancillary ligand.Other Cp ligands include but are not limited to porphyrins,phthalocyanines, corrins, and other polyazamacrocycles.

In another aspect, the unbridged metallocene catalyst component isrepresented by the formula (D):Cp^(A)Cp^(B)ZrX_(q)  (D)wherein X and q are as described above, preferably q is 1 or 2, and eachCp^(A) and Cp^(B) in formula (D) is independently as defined for Cpabove and may be the same or different cyclopentadienyl ligands orligands isolobal to cyclopentadienyl, either or both of which maycontain heteroatoms and either or both of which may be substituted by agroup R. In one embodiment, Cp^(A) and Cp^(B) are independently selectedfrom the group consisting of cyclopentadienyl, indenyl,tetrahydroindenyl, fluorenyl, and substituted derivatives of each.

Independently, each Cp^(A) and Cp^(B) of formula (D) may beunsubstituted or substituted with any one or combination of substituentgroups R. Non-limiting examples of substituent groups R as used instructure (D) include hydrogen radicals, hydrocarbyls, lowerhydrocarbyls, substituted hydrocarbyls, heterohydrocarbyls, alkyls,lower alkyls, substituted alkyls, heteroalkyls, alkenyls, loweralkenyls, substituted alkenyls, heteroalkenyls, alkynyls, loweralkynyls, substituted alkynyls, heteroalkynyls, alkoxys, lower alkoxys,aryloxys, hydroxyls, alkylthios, lower alkyls thios, arylthios, thioxys,aryls, substituted aryls, heteroaryls, aralkyls, aralkylenes, alkaryls,alkarylenes, halides, haloalkyls, haloalkenyls, haloalkynyls,heteroalkyls, heterocycles, heteroaryls, heteroatom-containing groups,silyls, boryls, phosphinos, phosphines, aminos, amines, cycloalkyls,acyls, aroyls, alkylthiols, dialkylamines, alkylamidos, alkoxycarbonyls,aryloxycarbonyls, carbomoyls, alkyl- and dialkyl-carbamoyls, acyloxys,acylaminos, aroylaminos, and combinations thereof.

Preferable examples of alkyl substituents R associated with formula (D)include methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclopentyl,cyclohexyl, benzyl, phenyl, methylphenyl, and tert-butylphenyl groupsand the like, including all their isomers, for example, tertiary-butyl,isopropyl, and the like. Other possible radicals include substitutedalkyls and aryls such as, for example, fluoromethyl, fluoroethyl,difluoroethyl, iodopropyl, bromohexyl, chlorobenzyl and hydrocarbylsubstituted organometalloid radicals including trimethylsilyl,trimethylgermyl, methyldiethylsilyl, and the like; andhalocarbyl-substituted organometalloid radicals includingtris(trifluoromethyl)silyl, methylbis(difluoromethyl)silyl,bromomethyldimethylgermyl, and the like; and disubstituted boronradicals including dimethylboron, for example; and disubstituted Group15 radicals including dimethylamine, dimethylphosphine, diphenylamine,methylphenylphosphine, Group 16 radicals including methoxy, ethoxy,propoxy, phenoxy, methylsulfide, and ethylsulfide. Other substituents Rinclude olefins such as, but not limited to, olefinically unsaturatedsubstituents including vinyl-terminated ligands, for example, 3-butenyl,2-propenyl, 5-hexenyl, and the like. In one embodiment, at least two Rgroups, two adjacent R groups in one embodiment, are joined to form aring structure having from 3 to 30 atoms selected from the groupconsisting of carbon, nitrogen, oxygen, phosphorous, silicon, germanium,aluminum, boron, and combinations thereof. Also, a substituent group R,such as 1-butanyl, may form a bonding association to the element M.

The ligands Cp^(A) and Cp^(B) of formula (D) are different from eachother in one embodiment, and the same in another embodiment.

It is contemplated that the metallocene catalyst components describedabove include their structural or optical or enantiomeric isomers(racemic mixture), and may be a pure enantiomer in one embodiment.

The unbridged metallocene catalyst component may comprise anycombination of any embodiments described herein.

Suitable unbridged metallocenes useful herein include, but are notlimited to, the metallocenes disclosed and referenced in the US patentscited above, as well as those disclosed and referenced in U.S. Pat. Nos.7,179,876; 7,169,864; 7,157,531; 7,129,302; 6,995,109; 6,958,306;6,884,748; 6,689,847; U.S. Patent Publication No. 2007/0055028, andpublished PCT Application Nos. WO 97/22635; WO 00/699/22; WO 01/30860;WO 01/30861; WO 02/46246; WO 02/50088; WO 04/026921; and WO 06/019494,all fully incorporated herein by reference. Additional catalystssuitable for use herein include those referenced in U.S. Pat. Nos.6,309,997; 6,265,338; U.S. Patent Publication No. 2006/019925, and thefollowing articles: Chem Rev 2000, 100, 1253; Resconi; Chem Rev 2003,103, 283; Chem Eur. J. 2006, 12, 7546 Mitsui; J Mol Catal A 2004, 213,141; Macromol Chem Phys, 2005, 206, 1847; and J Am Chem Soc 2001, 123,6847.

Exemplary unbridged metallocene compounds represented by formula (B)include: bis(cyclopentadienyl)zirconium dichloride;bis(cyclopentadienyl)zirconium dimethyl;bis(n-butylcyclopentadienyl)zirconium dichloride;bis(n-butylcyclopentadienyl)zirconium dimethyl;bis(pentamethylcyclopentadienyl)zirconium dichloride;bis(pentamethylcyclopentadienyl)zirconium dimethyl;bis(pentamethylcyclopentadienyl)hafnium dichloride;bis(pentamethylcyclopentadienyl)zirconium dimethyl;bis(1-methyl-3-n-butylcyclopentadienyl)zirconium dichloride;bis(1-methyl-3-n-butylcyclopentadienyl)zirconium dimethyl;bis(1-methyl-3-phenylcyclopentadienyl)zirconium dichloride;bis(1-methyl-3-phenylcyclopentadienyl)zirconium dimethyl;bis(1-methyl-3-n-butylcyclopentadienyl)hafnium dichloride;bis(1-methyl-3-n-butylcyclopentadienyl)zirconium dimethyl;bis(indenyl)zirconium dichloride; bis(indenyl)zirconium dimethyl;bis(tetrahydro-1-indenyl)zirconium dichloride;bis(tetrahydro-1-indenyl)zirconium dimethyl; (n-propylcyclopentadienyl)(pentamethyl cyclopentadienyl)zirconium dichloride;(n-propyl cyclopentadienyl)(pentamethyl cyclopentadienyl)zirconiumdimethyl; rac/meso-bis(1-ethylindenyl)zirconium dichloride;rac/meso-bis(1-ethylindenyl)zirconium dimethyl;rac/meso-bis(1-methylindenyl)zirconium dichloride;rac/meso-bis(1-methylindenyl)zirconium dimethyl;rac/meso-bis(1-propylindenyl)zirconium dichloride;rac/meso-bis(1-propylindenyl)zirconium dimethyl;rac/meso-bis(1-butylindenyl)zirconium dichloride;rac/meso-bis(1-butylindenyl)zirconium dimethyl; meso-bis(1-ethylindenyl)zirconium dichloride; meso-bis(1ethylindenyl) zirconium dimethyl;(1-methylindenyl)(pentamethyl cyclopentadienyl) zirconium dichloride;and (1-methylindenyl)(pentamethyl cyclopentadienyl) zirconium dimethyland the alkyl or halide versions thereof where the Me₂ or Cl₂ in thelist above is replaced with Bz₂, Et₂, Ph₂, Br₂ or I₂.

Preferred unbridged metallocene compounds useful herein are include:bis(cyclopentadienyl)zirconium dichloride;bis(n-butylcyclopentadienyl)zirconium dichloride;bis(n-butylcyclopentadienyl)zirconium dimethyl;bis(pentamethylcyclopentadienyl)zirconium dichloride;bis(pentamethylcyclopentadienyl)zirconium dimethyl;bis(pentamethylcyclopentadienyl)hafnium dichloride;bis(pentamethylcyclopentadienyl)zirconium dimethyl;bis(1-methyl-3-n-butylcyclopentadienyl)zirconium dichloride;bis(1-methyl-3-n-butylcyclopentadienyl)zirconium dimethyl;bis(1-methyl-3-n-butylcyclopentadienyl)hafnium dichloride;bis(1-methyl-3-n-butylcyclopentadienyl)zirconium dimethyl;bis(indenyl)zirconium dichloride, bis(indenyl)zirconium dimethyl;bis(tetrahydro-1-indenyl)zirconium dichloride;bis(tetrahydro-1-indenyl)zirconium dimethyl; (n-propylcyclopentadienyl)(pentamethyl cyclopentadienyl)zirconium dichloride;(n-propyl cyclopentadienyl)(pentamethyl cyclopentadienyl)zirconiumdimethyl; rac/meso-bis(1-ethylindenyl)zirconium dichloride;rac/meso-bis(1-methylindenyl)zirconium dichloride;rac/meso-bis(1-propylindenyl)zirconium dichloride;meso-bis(1ethylindenyl) zirconium dichloride, and(1-methylindenyl)(pentamethyl cyclopentadienyl)zirconium dichloride, andthe alkyl or halide versions thereof where the Me₂ or Cl₂ in the listabove is replaced with Bz₂, Et₂, Ph₂, Br₂, or I₂.

Support Material

In embodiments of the present invention, the catalyst systems comprise asupport material. Preferably, the support material is a porous supportmaterial, for example, talc, and inorganic oxides. Other supportmaterials include zeolites, clays, organoclays, or any other organic orinorganic support material, or mixtures thereof. As used herein,“support” and “support material” are used interchangeably.

Preferably, the support material is an inorganic oxide in a finelydivided form. Suitable inorganic oxide materials for use in thesupported catalyst systems herein include Groups 2, 4, 13, and 14 metaloxides such as silica, alumina, and mixtures thereof. Other inorganicoxides that may be employed, either alone or in combination, with thesilica or alumina are magnesia, titania, zirconia, and the like. Othersuitable support materials, however, can be employed, for example,finely divided functionalized polyolefins such as finely dividedpolyethylene. Particularly useful supports include magnesia, titania,zirconia, montmorillonite, phyllosilicate, zeolites, talc, clays, andthe like. Also, combinations of these support materials may be used, forexample, silica-chromium, silica-alumina, silica-titania, and the like.Preferred support materials include Al₂O₃, ZrO₂, SiO₂, and combinationsthereof, more preferably, SiO₂, Al₂O₃, or SiO₂/Al₂O₃.

It is preferred that the support material, most preferably, an inorganicoxide, has a surface area in the range of from about 10 m²/g to about700 m²/g, pore volume in the range of from about 0.1 cc/g to about 4.0cc/g, and average particle size in the range of from about 5 m to about500 m. More preferably, the surface area of the support material is inthe range of from about 50 m²/g to about 500 m²/g, pore volume of fromabout 0.5 cc/g to about 3.5 cc/g, and average particle size of fromabout 10 m to about 200 m. Most preferably, the surface area of thesupport material is in the range of from about 100 m²/g to about 400m²/g, pore volume from about 0.8 cc/g to about 3.0 cc/g, and averageparticle size is from about 5 m to about 100 μm. The average pore sizeof the support material can be from 10 to 1,000 Å, preferably, 50 toabout 500 Å, and most preferably, 75 to about 350 Å. In someembodiments, the support material is a high surface area, amorphoussilica (surface area ≥300 m²/gm, pore volume ≥1.65 cm³/gm), and ismarketed under the tradenames of DAVISON 952 or DAVISON 955 by theDavison Chemical Division of W. R. Grace and Company, are particularlyuseful. In other embodiments, DAVIDSON 948 is used.

In some embodiments of the present invention, the support material maybe dry, that is, free of absorbed water. Drying of the support materialcan be achieved by heating or calcining at about 100° C. to about 1000°C., preferably, at least about 600° C. When the support material issilica, it is typically heated to at least 200° C., preferably, about200° C. to about 850° C., and most preferably, at about 600° C.; and fora time of about 1 minute to about 100 hours, from about 12 hours toabout 72 hours, or from about 24 hours to about 60 hours. The calcinedsupport material, preferably, has at least some reactive hydroxyl (OH)groups.

In a particularly useful embodiment, the support material is fluorided.Fluoriding agent containing compounds may be any compound containing afluorine atom. Particularly desirable are inorganic fluorine containingcompounds are selected from the group consisting of NH₄BF₄, (NH₄)₂SiF₆,NH₄PF₆, NH₄F, (NH₄)₂TaF₇, NH₄NbF₄, (NH₄)₂GeF₆, (NH₄)₂SmF₆, (NH₄)₂TiF₆,(NH₄)₂ZrF₆, MoF₆, ReF₆, GaF₃, SO₂ClF, F₂, SiF₄, SF₆, ClF₃, ClF₅, BrF5,IF₇, NF₃, HF, BF₃, NHF₂ and NH₄HF₂. Of these, ammoniumhexafluorosilicate and ammonium tetrafluoroborate are useful.Combinations of these compounds may also be used.

Ammonium hexafluorosilicate and ammonium tetrafluoroborate fluorinecompounds are typically solid particulates as are the silicon dioxidesupports. A desirable method of treating the support with the fluorinecompound is to dry mix the two components by simply blending at aconcentration of from 0.01 to 10.0 millimole F/g of support, desirablyin the range of from 0.05 to 6.0 millimole F/g of support, and mostdesirably in the range of from 0.1 to 3.0 millimole F/g of support. Thefluorine compound can be dry mixed with the support either before orafter charging to a vessel for dehydration or calcining the support.Accordingly, the fluorine concentration present on the support is in therange of from 0.1 to 25 wt %, alternatively from 0.19 to 19 wt %,alternatively from 0.6 to 3.5 wt %, based upon the weight of thesupport.

The above two metal catalyst components described herein are generallydeposited on the support material at a loading level of 10-100micromoles of metal per gram of solid support; alternatively 20-80micromoles of metal per gram of solid support; or 40-60 micromoles ofmetal per gram of support. But greater or lesser values may be usedprovided that the total amount of solid complex does not exceed thesupport's pore volume.

In at least one embodiment, the support material comprises a supportmaterial treated with an electron-withdrawing anion. The supportmaterial can be silica, alumina, silica-alumina, silica-zirconia,alumina-zirconia, aluminum phosphate, heteropolytungstates, titania,magnesia, boria, zinc oxide, mixed oxides thereof, or mixtures thereof;and the electron-withdrawing anion is selected from fluoride, chloride,bromide, phosphate, triflate, bisulfate, sulfate, or any combinationthereof.

The electron-withdrawing component used to treat the support materialcan be any component that increases the Lewis or Brønsted acidity of thesupport material upon treatment (as compared to the support materialthat is not treated with at least one electron-withdrawing anion). In atleast one embodiment, the electron-withdrawing component is anelectron-withdrawing anion derived from a salt, an acid, or othercompound, such as a volatile organic compound, that serves as a sourceor precursor for that anion. Electron-withdrawing anions can be sulfate,bisulfate, fluoride, chloride, bromide, iodide, fluorosulfate,fluoroborate, phosphate, fluorophosphate, trifluoroacetate, triflate,fluorozirconate, fluorotitanate, phospho-tungstate, or mixtures thereof,or combinations thereof. An electron-withdrawing anion can be fluoride,chloride, bromide, phosphate, triflate, bisulfate, or sulfate, and thelike, or any combination thereof, at least one embodiment of thisinvention. In at least one embodiment, the electron-withdrawing anion issulfate, bisulfate, fluoride, chloride, bromide, iodide, fluorosulfate,fluoroborate, phosphate, fluorophosphate, trifluoroacetate, triflate,fluorozirconate, fluorotitanate, or combinations thereof.

Thus, for example, the support material suitable for use in the catalystsystems of the present invention can be one or more of fluoridedalumina, chlorided alumina, bromided alumina, sulfated alumina,fluorided silica-alumina, chlorided silica-alumina, bromidedsilica-alumina, sulfated silica-alumina, fluorided silica-zirconia,chlorided silica-zirconia, bromided silica-zirconia, sulfatedsilica-zirconia, fluorided silica-titania, fluorided silica-coatedalumina, sulfated silica-coated alumina, phosphated silica-coatedalumina, and the like, or combinations thereof. In at least oneembodiment, the activator-support can be, or can comprise, fluoridedalumina, sulfated alumina, fluorided silica-alumina, sulfatedsilica-alumina, fluorided silica-coated alumina, sulfated silica-coatedalumina, phosphated silica-coated alumina, or combinations thereof. Inanother embodiment, the support material includes alumina treated withhexafluorotitanic acid, silica-coated alumina treated withhexafluorotitanic acid, silica-alumina treated with hexafluorozirconicacid, silica-alumina treated with trifluoroacetic acid, fluoridedboria-alumina, silica treated with tetrafluoroboric acid, aluminatreated with tetrafluoroboric acid, alumina treated withhexafluorophosphoric acid, or combinations thereof. Further, any ofthese activator-supports optionally can be treated with a metal ion.

Non-limiting examples of cations suitable for use in the presentdisclosure in the salt of the electron-withdrawing anion includeammonium, trialkyl ammonium, tetraalkyl ammonium, tetraalkylphosphonium, H+, [H(OEt₂)₂]+, or combinations thereof.

Further, combinations of one or more different electron-withdrawinganions, in varying proportions, can be used to tailor the specificacidity of the support material to a desired level. Combinations ofelectron-withdrawing components can be contacted with the supportmaterial simultaneously or individually, and in any order that providesa desired chemically-treated support material acidity. For example, inat least one embodiment, two or more electron-withdrawing anion sourcecompounds in two or more separate contacting steps.

In one embodiment of the present invention, one example of a process bywhich a chemically-treated support material is prepared is as follows: aselected support material, or combination of support materials, can becontacted with a first electron-withdrawing anion source compound toform a first mixture; such first mixture can be calcined and thencontacted with a second electron-withdrawing anion source compound toform a second mixture; the second mixture can then be calcined to form atreated support material. In such a process, the first and secondelectron-withdrawing anion source compounds can be either the same ordifferent compounds.

The method by which the oxide is contacted with the electron-withdrawingcomponent, typically a salt or an acid of an electron-withdrawing anion,can include, but is not limited to, gelling, co-gelling, impregnation ofone compound onto another, and the like, or combinations thereof.Following a contacting method, the contacted mixture of the supportmaterial, electron-withdrawing anion, and optional metal ion, can becalcined.

According to another embodiment of the present invention, the supportmaterial can be treated by a process comprising: (i) contacting asupport material with a first electron-withdrawing anion source compoundto form a first mixture; (ii) calcining the first mixture to produce acalcined first mixture; (iii) contacting the calcined first mixture witha second electron-withdrawing anion source compound to form a secondmixture; and (iv) calcining the second mixture to form the treatedsupport material.

Activators

The supported catalyst systems may be formed by combining the above twometal catalyst components with activators in any manner known from theliterature including by supporting them for use in slurry or gas phasepolymerization. Activators are defined to be any compound which canactivate any one of the catalyst compounds described above by convertingthe neutral metal catalyst compound to a catalytically active metalcatalyst compound cation. Non-limiting activators, for example, includealumoxanes, aluminum alkyls, ionizing activators, which may be neutralor ionic, and conventional-type cocatalysts. Preferred activatorstypically include alumoxane compounds, modified alumoxane compounds, andionizing anion precursor compounds that abstract a reactive, σ-bound,metal ligand making the metal compound cationic and providing acharge-balancing non-coordinating or weakly coordinating anion.

Alumoxane Activators

Alumoxane activators are utilized as activators in the catalyst systemsdescribed herein. Alumoxanes are generally oligomeric compoundscontaining —Al(R¹)—O— sub-units, where R¹ is an alkyl group. Examples ofalumoxanes include methylalumoxane (MAO), modified methylalumoxane(MMAO), ethylalumoxane and isobutylalumoxane. Alkylalumoxanes andmodified alkylalumoxanes are suitable as catalyst activators,particularly when the abstractable ligand is an alkyl, halide, alkoxide,or amide. Mixtures of different alumoxanes and modified alumoxanes mayalso be used. It may be preferable to use a visually clearmethylalumoxane. A cloudy or gelled alumoxane can be filtered to producea clear solution or clear alumoxane can be decanted from the cloudysolution. A useful alumoxane is a modified methyl alumoxane (MMAO)cocatalyst type 3A (commercially available from Akzo Chemicals, Inc.under the trade name Modified Methylalumoxane type 3A, covered underU.S. Pat. No. 5,041,584).

When the activator is an alumoxane (modified or unmodified), someembodiments select the maximum amount of activator typically at up to a5000-fold molar excess Al/M over the catalyst (per metal catalyticsite). The minimum activator-to-catalyst-compound is a 1:1 molar ratio.Alternate preferred ranges include from 1:1 to 500:1, alternatively from1:1 to 200:1, alternatively from 1:1 to 100:1, or alternatively from 1:1to 50:1.

In an alternate embodiment, little or no alumoxane is used in thepolymerization processes described herein. Preferably, alumoxane ispresent at zero mol %, alternatively the alumoxane is present at a molarratio of aluminum to catalyst compound transition metal less than 500:1,preferably less than 300:1, preferably less than 100:1, preferably lessthan 1:1.

Non Coordinating Anion Activators

The term “non-coordinating anion” (NCA) means an anion which either doesnot coordinate to a cation or which is only weakly coordinated to acation thereby remaining sufficiently labile to be displaced by aneutral Lewis base. “Compatible” non-coordinating anions are those whichare not degraded to neutrality when the initially formed complexdecomposes. Further, the anion will not transfer an anionic substituentor fragment to the cation so as to cause it to form a neutral transitionmetal compound and a neutral by-product from the anion. Non-coordinatinganions useful in accordance with embodiments of the present disclosureare those that are compatible, stabilize the transition metal cation inthe sense of balancing its ionic charge at +1, and yet retain sufficientlability to permit displacement during polymerization.

It is within the scope of the present invention to use an ionizingactivator, neutral or ionic, such as tri (n-butyl) ammonium tetrakis(pentafluorophenyl) borate, a tris perfluorophenyl boron metalloidprecursor or a tris perfluoronaphthyl boron metalloid precursor,polyhalogenated heteroborane anions (WO 98/43983), boric acid (U.S. Pat.No. 5,942,459), or combination thereof. It is also within the scope ofthe present invention to use neutral or ionic activators alone or incombination with alumoxane or modified alumoxane activators.

For descriptions of useful activators please see U.S. Pat. Nos.8,658,556 and 6,211,105.

Preferred activators include N,N-dimethylaniliniumtetrakis(perfluoronaphthyl)borate, N,N-dimethylaniliniumtetrakis(perfluorobiphenyl)borate, N,N-dimethylaniliniumtetrakis(perfluorophenyl)borate, N,N-dimethylaniliniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triphenylcarbeniumtetrakis(perfluoronaphthyl)borate, triphenylcarbeniumtetrakis(perfluorobiphenyl)borate, triphenylcarbeniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triphenylcarbeniumtetrakis(perfluorophenyl)borate, [Me₃NH⁺][B(C₆F₅)₄ ⁻ ],1-(4-(tris(pentafluorophenyl)borate)-2,3,5,6-tetrafluorophenyl)pyrrolidinium;and [Me₃NH⁺][B(C₆F₅)₄ ⁻ ],1-(4-(tris(pentafluorophenyl)borate)-2,3,5,6-tetrafluorophenyl)pyrrolidinium; and sodium tetrakis(pentafluorophenyl)borate, potassiumtetrakis(pentafluorophenyl)borate,4-(tris(pentafluorophenyl)borate)-2,3,5,6-tetrafluoropyridinium,solidium tetrakis(perfluorophenyl)aluminate, potassiumterakis(pentafluorophenyl), and N,N-dimethylaniliniumtetrakis(perfluorophenyl)aluminate.

In a preferred embodiment, the activator comprises a triaryl carbonium(such as triphenylcarbenium tetraphenylborate, triphenylcarbeniumtetrakis(pentafluorophenyl)borate, triphenylcarbeniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, triphenylcarbeniumtetrakis(perfluoronaphthyl)borate, triphenylcarbeniumtetrakis(perfluorobiphenyl)borate, triphenylcarbeniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate).

In another embodiment, the activator comprises one or more oftrialkylammonium tetrakis(pentafluorophenyl)borate, N,N-dialkylaniliniumtetrakis(pentafluorophenyl)borate,N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(pentafluorophenyl)borate, trialkylammoniumtetrakis-(2,3,4,6-tetrafluorophenyl) borate, N,N-dialkylaniliniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, trialkylammoniumtetrakis(perfluoronaphthyl)borate, N,N-dialkylaniliniumtetrakis(perfluoronaphthyl)borate, trialkylammoniumtetrakis(perfluorobiphenyl)borate, N,N-dialkylaniliniumtetrakis(perfluorobiphenyl)borate, trialkylammoniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, N,N-dialkylaniliniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate,N,N-dialkyl-(2,4,6-trimethylanilinium)tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, di-(i-propyl) ammoniumtetrakis(pentafluorophenyl)borate, (where alkyl is methyl, ethyl,propyl, n-butyl, sec-butyl, or t-butyl).

The typical activator-to-catalyst ratio, e.g., all NCAactivators-to-catalyst ratio is about a 1:1 molar ratio. Alternatepreferred ranges include from 0.1:1 to 100:1, alternatively from 0.5:1to 200:1, alternatively from 1:1 to 500:1 alternatively from 1:1 to1000:1. A particularly useful range is from 0.5:1 to 10:1, preferably1:1 to 5:1.

Optional Scavengers or Co-Activators

In addition to the activator compounds, scavengers, chain transferagents or co-activators may be used. Aluminum alkyl or organoaluminumcompounds which may be utilized as co-activators include, for example,trimethylaluminum, triethylaluminum, triisobutylaluminum,tri-n-hexylaluminum, tri-n-octylaluminum, diethyl zinc, tri-n-butylaluminum, di-isobutyl aluminum hydride, or combinations thereof.

In some embodiments, the catalyst systems will additionally comprise oneor more scavenging compounds. Here, the term “scavenger” means acompound that removes polar impurities from the reaction environment.These impurities adversely affect catalyst activity and stability.Typically, the scavenging compound will be an organometallic compoundsuch as the Group-13 organometallic compounds of U.S. Pat. Nos.5,153,157; 5,241,025; and PCT Publication Nos. WO 91/09882; WO 94/03506;WO 93/14132; and WO 95/07941. Exemplary compounds include triethylaluminum, triethyl borane, tri-iso-butyl aluminum, methyl alumoxane,iso-butyl alumoxane, and tri-n-octyl aluminum. Those scavengingcompounds having bulky or C₆-C₂₀ linear hydrocarbyl substituentsconnected to the metal or metalloid center usually minimize adverseinteraction with the active catalyst. Examples include triethylaluminum, but more preferably, bulky compounds such as tri-iso-butylaluminum, tri-iso-prenyl aluminum, and long-chain linearalkyl-substituted aluminum compounds, such as tri-n-hexyl aluminum,tri-n-octyl aluminum, or tri-n-dodecyl aluminum. When alumoxane is usedas the activator, any excess over that needed for activation willscavenge impurities and additional scavenging compounds may beunnecessary. Alumoxanes also may be added in scavenging quantities withother activators, e.g., methylalumoxane, [Me₂HNPh]⁺[B(pfp)₄]⁻ or B(pfp)₃(perfluorophenyl=pfp=C₆F₅).

Preferred aluminum scavengers include those where there is oxygenpresent. That is, the material per se or the aluminum mixture used as ascavenger, includes an aluminum/oxygen species, such as an alumoxane oralkylaluminum oxides, e.g., dialkyaluminum oxides, such asbis(diisobutylaluminum) oxide. In one aspect, aluminum containingscavengers can be represented by the formula ((R_(z)—Al—)_(y)O—)_(x),wherein z is 1-2, y is 1-2, x is 1-100, and R is a C₁-C₁₂ hydrocarbylgroup. In another aspect, the scavenger has an oxygen to aluminum (O/Al)molar ratio of from about 0.25 to about 1.5, more particularly fromabout 0.5 to about 1.

Preparation of Mixed Catalyst Systems

The above two metal catalyst compounds can be combined to form a mixedcatalyst system.

The two or more metal catalyst compounds can be added together in adesired ratio when combined, contacted with an activator, or contactedwith a support material or a supported activator. The metal catalystcompounds may be added to the mixture sequentially or at the same time.

The ratio of catalyst (A):(B) can vary depending on the balance ofprocessability versus physical characteristics of the desired polymer.For example, the ratio (A):(B) can range from 1:10 to 10:1, such as 5:1to 1:5 or 1:1.

Alternative preparations can include addition of a first metal catalystcompound to a slurry including a support or a supported activatormixture for a specified reaction time, followed by the addition of thesecond metal catalyst compound solution, mixed for another specifiedtime, after which the mixture may be recovered for use in apolymerization reactor, such as by spray drying. Lastly, anotheradditive, such as 1-hexene in about 10 vol % can be present in themixture prior to the addition of the first metal catalyst compound.

The first metal catalyst compound may be supported via contact with asupport material for a reaction time. The resulting supported catalystcomposition may then be mixed with mineral oil to form a slurry, whichmay or may not include an activator. The slurry may then be admixed witha second metal catalyst compound prior to introduction of the resultingmixed catalyst system to a polymerization reactor. The second metalcatalyst compound may be admixed at any point prior to introduction tothe reactor, such as in a polymerization feed vessel or in-line in acatalyst delivery system.

The mixed catalyst system may be formed by combining a first metalcatalyst compound (for example a metal catalyst compound useful forproducing a first polymer attribute, such as a high molecular weightpolymer fraction or high comonomer content) with a support andactivator, desirably in a first diluent such as an alkane or toluene, toproduce a supported, activated catalyst compound. The supportedactivated catalyst compound, either isolated from the first diluent ornot, is then combined in one embodiment with a high viscosity diluentsuch as mineral or silicon oil, or an alkane diluent comprising from 5to 99 wt % mineral or silicon oil to form a slurry of the supportedmetal catalyst compound, followed by, or simultaneous to combining witha second metal catalyst compound (for example, a metal catalyst compounduseful for producing a second polymer attribute, such as a low molecularweight polymer fraction or low comonomer content), either in a diluentor as the dry solid compound, to form a supported activated mixedcatalyst system (“mixed catalyst system”). The mixed catalyst systemthus produced may be a supported and activated first metal catalystcompound in a slurry, the slurry comprising mineral or silicon oil, witha second metal catalyst compound that is not supported and not combinedwith additional activator, where the second metal catalyst compound mayor may not be partially or completely soluble in the slurry. In oneembodiment, the diluent consists of mineral oil.

Mineral oil, or “high viscosity diluents,” as used herein refers topetroleum hydrocarbons and mixtures of hydrocarbons that may includealiphatic, aromatic, and/or paraffinic components that are liquids at23° C. and above, and typically have a molecular weight of at least 300amu to 500 amu or more, and a viscosity at 40° C. of from 40 to 300 cStor greater, or from 50 to 200 cSt in a particular embodiment. The term“mineral oil” includes synthetic oils or liquid polymers, polybutenes,refined naphthenic hydrocarbons, and refined paraffins known in the art,such as disclosed in BLUE BOOK 2001, MATERIALS, COMPOUNDING INGREDIENTS,MACHINERY AND SERVICES FOR RUBBER 189 247 (J. H. Lippincott, D. R.Smith, K. Kish & B. Gordon eds. Lippincott & Peto Inc. 2001). Preferredmineral and silicon oils are those that exclude moieties that arereactive with metallocene catalysts, examples of which include hydroxyland carboxyl groups.

The diluent may comprise a blend of a mineral, silicon oil, and/or and ahydrocarbon selected from the group consisting of C₁ to C₁₀ alkanes, C₆to C₂₀ aromatic hydrocarbons, C₇ to C₂₁ alkyl-substituted hydrocarbons,and mixtures thereof. When the diluent is a blend comprising mineraloil, the diluent may comprise from 5 to 99 wt % mineral oil. In someembodiments, the diluent may consist essentially of mineral oil.

In one embodiment, the first metal catalyst compound is combined with anactivator and a first diluent to form a catalyst slurry that is thencombined with a support material. Until such contact is made, thesupport particles are preferably not previously activated. The firstmetal catalyst compound can be in any desirable form such as a drypowder, suspension in a diluent, solution in a diluent, liquid, etc. Thecatalyst slurry and support particles are then mixed thoroughly, in oneembodiment at an elevated temperature, so that both the first metalcatalyst compound and the activator are deposited on the supportparticles to form a support slurry.

After the first metal catalyst compound and activator are deposited onthe support, a second metal catalyst compound may then be combined withthe supported first metal catalyst compound, wherein the second iscombined with a diluent comprising mineral or silicon oil by anysuitable means either before, simultaneous to, or after contacting thesecond metal catalyst compound with the supported first metal catalystcompound. In one embodiment, the first metal catalyst compound isisolated form the first diluent to a dry state before combining with thesecond metal catalyst compound. Preferably, the second metal catalystcompound is not activated, that is, not combined with any activator,before being combined with the supported first metal catalyst compound.The resulting solids slurry (including both the supported first andsecond metal catalyst compounds) is then preferably, mixed thoroughly atan elevated temperature.

A wide range of mixing temperatures may be used at various stages ofmaking the mixed catalyst system. For example, in a specific embodiment,when the first metal catalyst compound and at least one activator, suchas methylalumoxane, are combined with a first diluent to form a mixture,the mixture is preferably, heated to a first temperature of from 25° C.to 150° C., preferably, from 50° C. to 125° C., more preferably, from75° C. to 100° C., most preferably, from 80° C. to 100° C. and stirredfor a period of time from 30 seconds to 12 hours, preferably, from 1minute to 6 hours, more preferably, from 10 minutes to 4 hours, and mostpreferably, from 30 minutes to 3 hours.

Next, that mixture is combined with a support material to provide afirst support slurry. The support material can be heated, or dehydratedif desired, prior to combining. In one or more embodiments, the firstsupport slurry is mixed at a temperature greater than 50° C.,preferably, greater than 70° C., more preferably, greater than 80° C.and most preferably, greater than 85° C., for a period of time from 30seconds to 12 hours, preferably, from 1 minute to 6 hours, morepreferably, from 10 minutes to 4 hours, and most preferably, from 30minutes to 3 hours. Preferably, the support slurry is mixed for a timesufficient to provide a collection of activated support particles thathave the first metal catalyst compound deposited thereto. The firstdiluent can then be removed from the first support slurry to provide adried supported first catalyst compound. For example, the first diluentcan be removed under vacuum or by nitrogen purge.

Next, the second metal catalyst compound is combined with the activatedfirst metal catalyst compound in the presence of a diluent comprisingmineral or silicon oil in one embodiment. Preferably, the second metalcatalyst compound is added in a molar ratio to the first metal catalystcompound in the range from 1:1 to 3:1. Most preferably, the molar ratiois approximately 1:1. The resultant slurry (or first support slurry) ispreferably, heated to a first temperature from 25° C. to 150° C.,preferably, from 50° C. to 125° C., more preferably, from 75° C. to 100°C., most preferably, from 80° C. to 100° C. and stirred for a period oftime from 30 seconds to 12 hours, preferably, from 1 minute to 6 hours,more preferably, from 10 minutes to 4 hours, and most preferably, from30 minutes to 3 hours.

The first diluent is an aromatic or alkane, preferably, hydrocarbondiluent having a boiling point of less than 200° C. such as toluene,xylene, hexane, etc., may be removed from the supported first metalcatalyst compound under vacuum or by nitrogen purge to provide asupported mixed catalyst system. Even after addition of the oil and/orthe second (or other) catalyst compound, it may be desirable to treatthe slurry to further remove any remaining solvents such as toluene.This can be accomplished by an N₂ purge or vacuum, for example.Depending upon the level of mineral oil added, the resultant mixedcatalyst system may still be a slurry or may be a free flowing powderthat comprises an amount of mineral oil. Thus, the mixed catalystsystem, while a slurry of solids in mineral oil in one embodiment, maytake any physical form such as a free flowing solid. For example, themixed catalyst system may range from 1 to 99 wt % solids content byweight of the mixed catalyst system (mineral oil, support, all catalystcompounds and activator(s)) in one embodiment. The metallocene compoundmay be the first or second compound, typically the second compound.

Polymerization Process

In at least one embodiment, a polymerization process includescontacting, in a reaction zone, a monomer (such as ethylene), and,optionally, comonomer (such as hexene), with a supported catalyst systemcomprising an unbridged group 4 (such as Hf) metallocene compoundrepresented by formula A, an unbridged group 4 (such as Zr) metallocenecompound represented by formula B, an activator, and a support materialas described above. A “reaction zone” also referred to as a“polymerization zone” is a vessel where polymerization takes place, forexample a batch reactor. When multiple reactors are used in eitherseries or parallel configuration, each reactor is considered as aseparate polymerization zone. For a multi-stage polymerization in both abatch reactor and a continuous reactor, each polymerization stage isconsidered as a separate polymerization zone. In at least oneembodiment, the polymerization occurs in one reaction zone. Usefulreaction zones include gas phase reactors, tubular reactors, continuousstirred tank reactors, etc.

Monomers useful herein include substituted or unsubstituted C₂ to C₄₀alpha olefins, preferably, C₂ to C₂₀ alpha olefins, preferably, C₂ toC₁₂ alpha olefins, preferably, ethylene, propylene, butene, pentene,hexene, heptene, octene, nonene, decene, undecene, dodecene and isomersthereof. In a preferred embodiment of the invention, the monomerscomprise ethylene and, optional, comonomers comprising one or more C₃ toC₄₀ olefins, preferably, C₄ to C₂₀ olefins, or preferably, C₆ to C₁₂olefins. The C₃ to C₄₀ olefin monomers may be linear, branched, orcyclic. The C₃ to C₄₀ cyclic olefins may be strained or unstrained,monocyclic or polycyclic, and may, optionally, include heteroatomsand/or one or more functional groups.

Exemplary C₃ to C₄₀ comonomers include propylene, butene, pentene,hexene, heptene, octene, nonene, decene, undecene, dodecene, norbornene,norbomadiene, dicyclopentadiene, cyclopentene, cycloheptene,cyclooctene, cyclooctadiene, cyclododecene, 7-oxanorbornene,7-oxanorbornadiene, substituted derivatives thereof, and isomersthereof, preferably, hexene, heptene, octene, nonene, decene, dodecene,cyclooctene, 1,5-cyclooctadiene, 1-hydroxy-4-cyclooctene,1-acetoxy-4-cyclooctene, 5-methylcyclopentene, cyclopentene,dicyclopentadiene, norbornene, norbomadiene, and their respectivehomologs and derivatives.

In a preferred embodiment, one or more dienes are present in the polymerproduced herein at up to 10 wt %, preferably, at 0.00001 to 1.0 wt %,preferably, 0.002 to 0.5 wt %, even more preferably, 0.003 to 0.2 wt %,based upon the total weight of the composition. In some embodiments 500ppm or less of diene is added to the polymerization, preferably, 400 ppmor less, preferably, or 300 ppm or less. In other embodiments, at least50 ppm of diene is added to the polymerization, or 100 ppm or more, or150 ppm or more.

Preferred diolefin monomers include any hydrocarbon structure,preferably, C₄ to C₃₀, having at least two unsaturated bonds, wherein atleast two of the unsaturated bonds are readily incorporated into apolymer by either a stereospecific or a non-stereospecific catalyst(s).It is further preferred that the diolefin monomers be selected fromalpha, omega-diene monomers (i.e., di-vinyl monomers). More preferably,the diolefin monomers are linear di-vinyl monomers, most preferably,those containing from 4 to 30 carbon atoms. Examples of preferred dienesinclude butadiene, pentadiene, hexadiene, heptadiene, octadiene,nonadiene, decadiene, undecadiene, dodecadiene, tridecadiene,tetradecadiene, pentadecadiene, hexadecadiene, heptadecadiene,octadecadiene, nonadecadiene, icosadiene, heneicosadiene, docosadiene,tricosadiene, tetracosadiene, pentacosadiene, hexacosadiene,heptacosadiene, octacosadiene, nonacosadiene, triacontadiene,particularly preferred dienes include 1,6-heptadiene, 1,7-octadiene,1,8-nonadiene, 1,9-decadiene, 1,10-undecadiene, 1,11-dodecadiene,1,12-tridecadiene, 1,13-tetradecadiene, and low molecular weightpolybutadienes (Mw less than 1000 g/mol). Preferred cyclic dienesinclude cyclopentadiene, vinylnorbornene, norbornadiene, ethylidenenorbornene, divinylbenzene, dicyclopentadiene or higher ring containingdiolefins with or without substituents at various ring positions.

In a particularly preferred embodiment, a process providespolymerization of ethylene and at least one comonomer having from 3 to 8carbon atoms, preferably, 4 to 8 carbon atoms. Particularly, thecomonomers are propylene, 1-butene, 4-methyl-1-pentene,3-methyl-1-pentene, 1-hexene and 1-octene, the most preferred being1-hexene, 1-butene and 1-octene.

In a particularly preferred embodiment, a process providespolymerization of one or more monomers selected from the groupconsisting of propylene, 1-butene, 1-pentene, 3-methyl-1-pentene,4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, and combinationsthereof.

Polymerization processes of the present disclosure can be carried out inany manner known in the art. Any suspension, homogeneous, bulk,solution, slurry, or gas phase polymerization process known in the artcan be used. Such processes can be run in a batch, semi-batch, orcontinuous mode. Gas phase polymerization processes and slurry processesare preferred. (A homogeneous polymerization process is preferably aprocess where at least 90 wt % of the product is soluble in the reactionmedia.) A bulk homogeneous process is particularly preferred. (A bulkprocess is preferably a process where monomer concentration in all feedsto the reactor is 70 volume % or more.) Alternatively, no solvent ordiluent is present or added in the reaction medium (except for the smallamounts used as the carrier for the catalyst system or other additives,or amounts typically found with the monomer; e.g., propane inpropylene).

In another embodiment, the process is a slurry process. As used herein,the term “slurry polymerization process” preferably means apolymerization process where a supported catalyst is employed andmonomers are polymerized on the supported catalyst particles. At least95 wt % of polymer products derived from the supported catalyst are ingranular form as solid particles (not dissolved in the diluent).

Suitable diluents/solvents for polymerization include non-coordinating,inert liquids. Examples include straight and branched-chainhydrocarbons, such as isobutane, butane, pentane, isopentane, hexanes,isohexane, heptane, octane, dodecane, and mixtures thereof; cyclic andalicyclic hydrocarbons, such as cyclohexane, cycloheptane,methylcyclohexane, methylcycloheptane, and mixtures thereof, such as canbe found commercially (Isopar™); perhalogenated hydrocarbons, such asperfluorided C₄₋₁₀ alkanes, chlorobenzene, and aromatic andalkylsubstituted aromatic compounds, such as benzene, toluene,mesitylene, and xylene. Suitable solvents also include liquid olefins,which may act as monomers or comonomers, including ethylene, propylene,1-butene, 1-hexene, 1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene,1-octene, 1-decene, and mixtures thereof. In a preferred embodiment,aliphatic hydrocarbon solvents are used as the solvent, such asisobutane, butane, pentane, isopentane, hexanes, isohexane, heptane,octane, dodecane, and mixtures thereof; cyclic and alicyclichydrocarbons, such as cyclohexane, cycloheptane, methylcyclohexane,methylcycloheptane, and mixtures thereof. In another embodiment, thesolvent is not aromatic, preferably, aromatics are present in thesolvent at less than 1 wt %, preferably, less than 0.5 wt %, preferably,less than 0 wt % based upon the weight of the solvents.

Gas Phase Polymerization

Generally, in a fluidized gas bed process used for producing polymers, agaseous stream containing one or more monomers is continuously cycledthrough a fluidized bed in the presence of a catalyst under reactiveconditions. The gaseous stream is withdrawn from the fluidized bed andrecycled back into the reactor. Simultaneously, polymer product iswithdrawn from the reactor and fresh monomer is added to replace thepolymerized monomer. (See, for example, U.S. Pat. Nos. 4,543,399;4,588,790; 5,028,670; 5,317,036; 5,352,749; 5,405,922; 5,436,304;5,453,471; 5,462,999; 5,616,661; and 5,668,228; all of which are fullyincorporated herein by reference.)

Slurry Phase Polymerization

A slurry polymerization process generally operates between 1 to about 50atmosphere pressure range (15 psi to 735 psi, 103 kPa to 5068 kPa) oreven greater and temperatures in the range of 0° C. to about 120° C. Ina slurry polymerization, a suspension of solid, particulate polymer isformed in a liquid polymerization diluent medium to which monomer andcomonomers, along with catalysts, are added. The suspension includingdiluent is intermittently or continuously removed from the reactor wherethe volatile components are separated from the polymer and recycled,optionally after a distillation, to the reactor. The liquid diluentemployed in the polymerization medium is typically an alkane having from3 to 7 carbon atoms, preferably a branched alkane. The medium employedshould be liquid under the conditions of polymerization and relativelyinert. When a propane medium is used, the process must be operated abovethe reaction diluent critical temperature and pressure. Preferably, ahexane or an isobutane medium is employed.

Polyolefin Products

The present invention further provides compositions of matter producedby the methods described herein.

In a preferred embodiment, the process described herein producesethylene homopolymers or ethylene copolymers, such asethylene-alpha-olefin (preferably C₃ to C₂₀) copolymers (such asethylene-butene copolymers, ethylene-hexene and/or ethylene-octenecopolymers) having an Mw/Mn of greater than 1 to 40 (preferably greaterthan 1 to 4, preferably greater than 1 to 3).

Likewise, processes of the present invention can form ethylenecopolymers. In a preferred embodiment, the copolymers produced hereinhave from 0 to 25 mol % (alternatively from 0.5 to 20 mol %,alternatively from 1 to 15 mol %, preferably from 3 to 10 mol %) of oneor more C₃ to C₂₀ olefin comonomer, such as a C₃-C₂₀ alpha-olefin,(preferably C₃ to C₁₂ alpha-olefin, preferably propylene, butene,hexene, octene, decene, dodecene, preferably propylene, butene, hexene,octene).

In a preferred embodiment, the monomer is ethylene and the comonomer ishexene, preferably from 1 to 15 mol % hexene, alternatively 1 to 10 mol%.

In particular, the present invention provides an in-situ ethylenepolymer composition having: 1) at least 50 mol % ethylene; and 2) adensity of 0.89 g/cc or more, preferably 0.935 g/cc or more (ASTM 1505).Preferably, the copolymer has higher comonomer (e.g., hexene) content inthe higher molecular weight (Mw) component of the resin as compared tothe lower molecular weight (Mw) component, preferably at least 10%higher, preferably at least 20% higher, preferably at least 30% higheras determined by GPC-4D. The dividing line between higher and lower Mwis the midpoint between the Mw's of two polymers each made using thesame polymerization conditions as the product made using the twocatalysts on a support, except that the first polymer is made withoutthe catalyst represented by formula (A) and the second polymer is madewithout the catalyst represented by formula (B). In the event a midpointcannot be determined, an Mw of 150,000 g/mol shall be used.

The copolymer produced herein typically has a composition distributionbreadth T₇₅-T₂₅, as measured by TREF, that is greater than 20° C.,preferably greater than 30° C., preferably greater than 40° C. TheT₇₅-T₂₅ value represents the homogeneity of the composition distributionas determined by temperature rising elution fractionation. A TREF curveis produced as described below. Then the temperature at which 75% of thepolymer is eluted is subtracted from the temperature at which 25% of thepolymer is eluted, as determined by the integration of the area underthe TREF curve. The T₇₅-T₂₅ value represents the difference. The closerthese temperatures comes together, the narrower the compositiondistribution.

Typically, the polymers produced herein have an Mw of 5,000 to 1,000,000g/mol (preferably 25,000 to 750,000 g/mol, preferably 50,000 to 500,000g/mol), and/or an Mw/Mn of greater than 1 to 40 (alternatively 1.2 to20, alternatively 1.3 to 10, alternatively 1.4 to 5, 1.5 to 4,alternatively 1.5 to 3) as determined by GPC-4D. Polymers producedherein typically have an Mz/Mw from about 1 to about 10, such as fromabout 2 to about 6, such as from about 3 to about 4, such as from about2 to about 3. Polymers produced herein typically have an Mz/Mn fromabout 1 to about 10, such as from about 2 to about 6, such as from about3 to about 5. The ratio of other average molecular weight ratios (e.g.,Mz/Mw) can be calculated to highlight how the distribution is affected.For instance, a trace amount of very high MW species in a polymerproduct can preferentially raise Mz more than Mw and, therefore, resultin a significantly higher ratio of Mz/Mw. Such difference in the effecton molecular weight distribution has been discovered to have profoundeffects on film toughness, such as tear property, through molecularorientation during the fabrication process.

In a preferred embodiment of the invention, the polymer produced hereinhas a unimodal or multimodal molecular weight distribution as determinedby Gel Permeation Chromatography (GPC). By “unimodal” is meant that theGPC trace has one peak or two inflection points. By “multimodal” ismeant that the GPC trace has at least two peaks or more than 2inflection points. An inflection point is that point where the secondderivative of the curve changes in sign (e.g., from negative to positiveor vice versa).

Usefully, in a preferred embodiment of the invention, the polymerproduced herein has a bimodal molecular weight distribution asdetermined by Gel Permeation Chromatography (GPC). By “bimodal” is meantthat the GPC trace has two peaks or at least 4 inflection points.

In another embodiment, the polymer produced herein has two peaks in theTREF measurement (see below). Two peaks in the TREF measurement as usedin this specification and the appended claims means the presence of twodistinct normalized IR response peaks in a graph of normalized IRresponse (vertical or y axis) versus elution temperature (horizontal orx axis with temperature increasing from left to right) using the TREFmethod below. A “peak” in this context means where the general slope ofthe graph changes from positive to negative with increasing temperature.Between the two peaks is a local minimum in which the general slope ofthe graph changes from negative to positive with increasing temperature.“General trend” of the graph is intended to exclude the multiple localminimums and maximums that can occur in intervals of 2° C. or less.Preferably, the two distinct peaks are at least 3° C. apart, morepreferably at least 4° C. apart, even more preferably at least 5° C.apart. Additionally, both of the distinct peaks occur at a temperatureon the graph above 20° C. and below 120° C. where the elutiontemperature is run to 0° C. or lower. This limitation avoids confusionwith the apparent peak on the graph at low temperature caused bymaterial that remains soluble at the lowest elution temperature. Twopeaks on such a graph indicates a bi-modal composition distribution(CD). An alternate method for TREF measurement can be used if the TREFmethod below does not show two peaks, i.e., see B. Monrabal,“Crystallization Analysis Fractionation: A New Technique for theAnalysis of Branching Distribution in Polyolefins,” Journal of AppliedPolymer Science, Vol. 52, 491-499 (1994).

TREF Method

Temperature Rising Elution Fractionation (TREF) analysis is done using aCrystallization Elution Fractionation (CEF) instrument from PolymerChar, S. A., Valencia, Spain. The principles of CEF analysis and ageneral description of the particular apparatus used are given in thearticle Monrabal, B. et al. Crystallization Elution Fractionation. A NewSeparation Process for Polyolefin Resins. Macromol. Symp., 2007, 257,71. In particular, a process conforming to the “TREF separation process”shown in FIG. 1a of this article, in which Fc=0, was used. Pertinentdetails of the analysis method and features of the apparatus used are asfollows.

The solvent used for preparing the sample solution and for elution was1,2-Dichlorobenzene (ODCB) which was stabilized by dissolving 1.6 g of2,6-bis(1,1-dimethylethyl)-4-methylphenol (butylated hydroxytoluene) ina 4-L bottle of fresh solvent at ambient temperature. The stabilizedsolvent was then filtered using a 0.1-μm Teflon filter (Millipore). Thesample (6-10 mg) to be analyzed was dissolved in 8 ml of ODCB metered atambient temperature by stirring (Medium setting) at 150° C. for 90 min.A small volume of the polymer solution was first filtered by an inlinefilter (stainless steel, 10 μm), which is back-flushed after everyfiltration. The filtrate was then used to completely fill a 200-μlinjection-valve loop. The volume in the loop was then introduced nearthe center of the CEF column (15-cm long SS tubing, ⅜″ o.d., 7.8 mmi.d.) packed with an inert support (SS balls) at 140° C., and the columntemperature was stabilized at 125° C. for 20 min. The sample volume wasthen allowed to crystallize in the column by reducing the temperature to0° C. at a cooling rate of 1° C./min. The column was kept at 0° C. for10 min before injecting the ODCB flow (1 ml/min) into the column for 10min to elute and measure the polymer that did not crystallize (solublefraction). The wide-band channel of the infrared detector used (PolymerChar IR5) generates an absorbance signal that is proportional to theconcentration of polymer in the eluting flow. A complete TREF curve wasthen generated by increasing the temperature of the column from 0 to140° C. at a rate of 2° C./min while maintaining the ODCB flow at 1ml/min to elute and measure the concentration of the dissolving polymer.

GPC 4D Procedure: Molecular Weight, Comonomer Composition and Long ChainBranching Determination by GPC-IR Hyphenated with Multiple Detectors

Unless otherwise indicated, the distributions and the moments ofmolecular weight (Mw, Mn, Mw/Mn, etc.), the comonomer content (C₂, C₃,C₆, etc.) and the branching index (g′_(vis)) are determined by using ahigh temperature Gel Permeation Chromatography (Polymer Char GPC-IR)equipped with a multiple-channel band-filter based Infrared detectorIR5, an 18-angle light scattering detector and a viscometer. ThreeAgilent PLgel 10-μm Mixed-B LS columns are used to provide polymerseparation. Aldrich reagent grade 1,2,4-trichlorobenzene (TCB) with 300ppm antioxidant butylated hydroxytoluene (BHT) is used as the mobilephase. The TCB mixture is filtered through a 0.1-μm Teflon filter anddegassed with an online degasser before entering the GPC instrument. Thenominal flow rate is 1.0 ml/min and the nominal injection volume is 200μL. The whole system including transfer lines, columns, and detectorsare contained in an oven maintained at 145° C. The polymer sample isweighed and sealed in a standard vial with 80-μL flow marker (Heptane)added to it. After loading the vial in the autosampler, polymer isautomatically dissolved in the instrument with 8 ml added TCB solvent.The polymer is dissolved at 160° C. with continuous shaking for about 1hour for most PE samples or 2 hour for PP samples. The TCB densitiesused in concentration calculation are 1.463 g/ml at room temperature and1.284 g/ml at 145° C. The sample solution concentration is from 0.2 to2.0 mg/ml, with lower concentrations being used for higher molecularweight samples. The concentration (c), at each point in the chromatogramis calculated from the baseline-subtracted IR5 broadband signalintensity (I), using the following equation: c=βI, where β is the massconstant. The mass recovery is calculated from the ratio of theintegrated area of the concentration chromatography over elution volumeand the injection mass which is equal to the pre-determinedconcentration multiplied by injection loop volume. The conventionalmolecular weight (IR MW) is determined by combining universalcalibration relationship with the column calibration which is performedwith a series of monodispersed polystyrene (PS) standards ranging from700 to 10M gm/mole. The MW at each elution volume is calculated withfollowing equation:

${\log\mspace{14mu} M} = {\frac{\log( {K_{PS}/K} )}{\alpha + 1} + {\frac{\alpha_{PS} + 1}{\alpha + 1}\log\mspace{14mu} M_{PS}}}$where the variables with subscript “PS” stand for polystyrene whilethose without a subscript are for the test samples. In this method,α_(PS)=0.67 and K_(PS)=0.000175 while α and K are for other materials ascalculated and published in literature (Sun, T. et al. Macromolecules,2001, 34, 6812), except that for purposes of the present invention,α=0.695 and K=0.000579 for linear ethylene polymers, α=0.705 andK=0.0002288 for linear propylene polymers, α=0.695 and K=0.000181 forlinear butene polymers, α is 0.695 and K is0.000579*(1-0.0087*w2b+0.000018*(w2b){circumflex over ( )}2) forethylene-butene copolymer where w2b is a bulk weight percent of butenecomonomer, α is 0.695 and K is 0.000579*(1-0.0075*w2b) forethylene-hexene copolymer where w2b is a bulk weight percent of hexenecomonomer, and α is 0.695 and K is 0.000579*(1-0.0077*w2b) forethylene-octene copolymer where w2b is a bulk weight percent of octenecomonomer. Concentrations are expressed in g/cm³, molecular weight isexpressed in g/mole, and intrinsic viscosity (hence K in theMark-Houwink equation) is expressed in dL/g unless otherwise noted.

The comonomer composition is determined by the ratio of the IR5 detectorintensity corresponding to CH₂ and CH₃ channel calibrated with a seriesof PE and PP homo/copolymer standards whose nominal value arepredetermined by NMR or FTIR. In particular, this provides the methylsper 1000 total carbons (CH₃/1000TC) as a function of molecular weight.The short-chain branch (SCB) content per 1000TC (SCB/1000TC) is thencomputed as a function of molecular weight by applying a chain-endcorrection to the CH₃/1000TC function, assuming each chain to be linearand terminated by a methyl group at each end. The weight % comonomer isthen obtained from the following expression in which f is 0.3, 0.4, 0.6,0.8, and so on for C₃, C₄, C₆, C₈, and so on co-monomers, respectively:w2=f*SCB/1000TC.

The bulk composition of the polymer from the GPC-IR and GPC-4D analysesis obtained by considering the entire signals of the CH₃ and CH₂channels between the integration limits of the concentrationchromatogram. First, the following ratio is obtained

${{Bulk}\mspace{14mu}{IR}\mspace{14mu}{ratio}} = {\frac{{Area}\mspace{14mu}{of}\mspace{14mu}{CH}_{3}\mspace{14mu}{signal}\mspace{14mu}{within}\mspace{14mu}{integration}\mspace{14mu}{limits}}{{Area}\mspace{14mu}{of}\mspace{14mu}{CH}_{2}\mspace{14mu}{signal}\mspace{14mu}{within}\mspace{14mu}{integration}\mspace{14mu}{limits}}.}$

Then the same calibration of the CH₃ and CH₂ signal ratio, as mentionedpreviously in obtaining the CH3/1000TC as a function of molecularweight, is applied to obtain the bulk CH3/1000TC. A bulk methyl chainends per 1000TC (bulk CH3end/1000TC) is obtained by weight-averaging thechain-end correction over the molecular-weight range. Thenw2b=f*bulk CH3/1000TCbulk SCB/1000TC=bulk CH3/1000TC−bulk CH3end/1000TCand bulk SCB/1000TC is converted to bulk w2 in the same manner asdescribed above.

The LS detector is the 18-angle Wyatt Technology High Temperature DAWNHELEOSII. The LS molecular weight (M) at each point in the chromatogramis determined by analyzing the LS output using the Zimm model for staticlight scattering (Light Scattering from Polymer Solutions; Huglin, M.B., Ed.; Academic Press, 1972.):

$\frac{K_{o}c}{\Delta\;{R(\theta)}} = {\frac{1}{{MP}(\theta)} + {2A_{2}{c.}}}$Here, ΔR(θ) is the measured excess Rayleigh scattering intensity atscattering angle θ, c is the polymer concentration determined from theIR5 analysis, A₂ is the second virial coefficient, P(θ) is the formfactor for a monodisperse random coil, and K_(o) is the optical constantfor the system:

$K_{o} = \frac{4\pi^{2}{n^{2}( {{{dn}/d}\; c} )}^{2}}{\lambda^{4}N_{A}}$where N_(A) is Avogadro's number, and (dn/dc) is the refractive indexincrement for the system. The refractive index, n=1.500 for TCB at 145°C. and λ=665 nm. For analyzing polyethylene homopolymers,ethylene-hexene copolymers, and ethylene-octene copolymers, dn/dc=0.1048ml/mg and A₂=0.0015; for analyzing ethylene-butene copolymers,dn/dc=0.1048*(1-0.00126*w2) ml/mg and A₂=0.0015 where w2 is weightpercent butene comonomer.

A high temperature Agilent (or Viscotek Corporation) viscometer, whichhas four capillaries arranged in a Wheatstone bridge configuration withtwo pressure transducers, is used to determine specific viscosity. Onetransducer measures the total pressure drop across the detector, and theother, positioned between the two sides of the bridge, measures adifferential pressure. The specific viscosity, η_(S), for the solutionflowing through the viscometer is calculated from their outputs. Theintrinsic viscosity, [η], at each point in the chromatogram iscalculated from the equation [η]=η_(S)/c, where c is concentration andis determined from the IR5 broadband channel output. The viscosity MW ateach point is calculated as M=K_(PS)M^(α) ^(PS) ⁺¹/[η], where α_(ps) is0.67 and K_(ps) is 0.000175.

The branching index (g′_(vis)) is calculated using the output of theGPC-IR5-LS-VIS method as follows. The average intrinsic viscosity,[η]_(avg), of the sample is calculated by:

$\lbrack\eta\rbrack_{avg} = \frac{\sum{c_{i}\lbrack\eta\rbrack}_{i}}{\sum c_{i}}$where the summations are over the chromatographic slices, i, between theintegration limits. The branching index g′_(vis) is defined as

${g_{vis}^{\prime} = \frac{\lbrack\eta\rbrack_{avg}}{{KM}_{v}^{\alpha}}},$where M_(V) is the viscosity-average molecular weight based on molecularweights determined by LS analysis and the K and α are for the referencelinear polymer, which are, for purposes of the present invention,α=0.695 and K=0.000579 for linear ethylene polymers, α=0.705 andK=0.0002288 for linear propylene polymers, α=0.695 and K=0.000181 forlinear butene polymers, α is 0.695 and K is0.000579*(1-0.0087*w2b+0.000018*(w2b){circumflex over ( )}) forethylene-butene copolymer where w2b is a bulk weight percent of butenecomonomer, α is 0.695 and K is 0.000579*(1-0.0075*w2b) forethylene-hexene copolymer where w2b is a bulk weight percent of hexenecomonomer, and α is 0.695 and K is 0.000579*(1-0.0077*w2b) forethylene-octene copolymer where w2b is a bulk weight percent of octenecomonomer. Concentrations are expressed in g/cm³, molecular weight isexpressed in g/mole, and intrinsic viscosity (hence K in theMark-Houwink equation) is expressed in dL/g unless otherwise noted.Calculation of the w2b values is as discussed above.

The reversed-co-monomer index (RCI,m) is computed from x2 (mol %co-monomer C₃, C₄, C₆, C₈, etc.), as a function of molecular weight,where x2 is obtained from the following expression in which n is thenumber of carbon atoms in the comonomer (3 for C₃, 4 for C₄, 6 for C₆,etc.):

${x\; 2} = {- {\frac{200\mspace{14mu} w\; 2}{{{- 100}\mspace{14mu} n} - {2\mspace{14mu} w\; 2} + {{nw}\; 2}}.}}$

Then the molecular-weight distribution, W(z) where z=log₁₀ M, ismodified to W′(z) by setting to 0 the points in W that are less than 5%of the maximum of W; this is to effectively remove points for which theS/N in the composition signal is low. Also, points of W′ for molecularweights below 2000 gm/mole are set to 0. Then W′ is renormalized so that1=∫_(−∞) ^(∞) W′dzand a modified weight-average molecular weight (M_(w)′) is calculatedover the effectively reduced range of molecular weights as follows:M _(w)′=∫_(−∞) ^(∞)10^(z) *W′dz.The RCI,m is then computed asRCI,m=∫ _(−∞) ^(∞) x2(10^(z) −M _(w)′)W′dz.

A reversed-co-monomer index (RCI,w) is also defined on the basis of theweight fraction co-monomer signal (w2/100) and is computed as follows:

${RCI},{w = {\int_{- \infty}^{\infty}{\frac{w\; 2}{100}( {10^{z} - M_{w}^{\prime}} )\ W^{\prime}{{dz}.}}}}$

Note that in the above definite integrals the limits of integration arethe widest possible for the sake of generality; however, in reality thefunction is only integrated over a finite range for which data isacquired, considering the function in the rest of the non-acquired rangeto be 0. Also, by the manner in which W′ is obtained, it is possiblethat W′ is a discontinuous function, and the above integrations need tobe done piecewise.

Three co-monomer distribution ratios are also defined on the basis ofthe % weight (w2) comonomer signal, denoted as CDR-1,w, CDR-2,w, andCDR-3,w, as follows:

${{CDR}\text{-}1},{w = \frac{w\; 2({Mz})}{w\; 2({Mw})}}$${{CDR}\text{-}2},{w = \frac{w\; 2({Mz})}{w\; 2( \frac{{Mw} + {Mn}}{2} )}}$${{CDR}\text{-}3},{w = \frac{w\; 2( \frac{{Mz} + {Mw}}{2} )}{w\; 2( \frac{{Mw} + {Mn}}{2} )}}$where w2(Mw) is the % weight co-monomer signal corresponding to amolecular weight of Mw, w2(Mz) is the % weight co-monomer signalcorresponding to a molecular weight of Mz, w2[(Mw+Mn)/2)] is the %weight co-monomer signal corresponding to a molecular weight of(Mw+Mn)/2, and w2[(Mz+Mw)/2] is the % weight co-monomer signalcorresponding to a molecular weight of Mz+Mw/2, where Mw is theweight-average molecular weight, Mn is the number-average molecularweight, and Mz is the z-average molecular weight.

Accordingly, the co-monomer distribution ratios can be also definedutilizing the % mole co-monomer signal, CDR-1,m, CDR-2,m, CDR-3,m, as:

${{CDR}\text{-}1},{m = \frac{x\; 2({Mz})}{x\; 2({Mw})}}$${{CDR}\text{-}2},{m = \frac{x\; 2({Mz})}{x\; 2( \frac{{Mw} + {Mn}}{2} )}}$${{CDR}\text{-}3},{m = \frac{x\; 2( \frac{{Mz} + {Mw}}{2} )}{x\; 2( \frac{{Mw} + {Mn}}{2} )}}$where x2(Mw) is the % mole co-monomer signal corresponding to amolecular weight of Mw, x2(Mz) is the % mole co-monomer signalcorresponding to a molecular weight of Mz, x2[(Mw+Mn)/2)] is the % moleco-monomer signal corresponding to a molecular weight of (Mw+Mn)/2, andx2[(Mz+Mw)/2] is the % mole co-monomer signal corresponding to amolecular weight of Mz+Mw/2, where Mw is the weight-average molecularweight, Mn is the number-average molecular weight, and Mz is thez-average molecular weight.

An “in-situ polymer composition” (also referred to as an “in-situ blend”or a “reactor blend”) is the composition which is the product of apolymerization with two catalyst compounds in the same reactor describedherein. Without wishing to be being bound by theory, it is thought thatthe two catalyst compounds produce a reactor blend (i.e., aninterpenetrating network) of two (or more) components made in the samereactors (or reactions zones) with the two catalysts. These sorts ofcompositions may be referred to as reactor blends, although the term maynot be strictly accurate since there may be polymer species comprisingcomponents produced by each catalyst compound that are not technically ablend.

An “ex-situ blend” is a blend which is a physical blend of two or morepolymers synthesized independently and then subsequently blendedtogether typically using a melt-mixing process, such as an extruder. Anex-situ blend is distinguished by the fact that the polymer componentsare collected in solid form after exiting their respective synthesisprocesses, and then combined to form the blend; whereas for an in-situpolymer composition, the polymer components are prepared within a commonsynthesis process and only the combination is collected in solid form.

In any embodiment described herein, the polymer composition produced isan in-situ polymer composition.

In at least one embodiment of the present invention, the polymerproduced is an in-situ polymer composition having an ethylene content of70 wt % or more, preferably 80 wt % or more, preferably 90 wt % or moreand/or a density of 0.910 or more, alternatively 0.93 g/cc or more;alternatively 0.935 g/cc or more, alternatively 0.938 g/cc or more.

In at least one embodiment of the present invention, the polymerproduced is an in-situ polymer composition having a density of 0.890g/cc or more, alternatively from 0.935 to 0.960 g/cc.

In at least one embodiment of the present invention, the polymerproduced by the processes described herein comprises ethylene and one ormore comonomers and the polymer has: 1) an RCI,m greater than 30(alternatively greater than 30 to 50), an Mw/Mn of greater than 1, suchas from 1 to 15, or 2.3 to 15, or 3 to 15, and optionally a T₇₅-T₂₅ of15 to 20° C.; or 2) an RCI,m greater than 50 (alternatively greater than80), an Mw/Mn of greater than 5 (alternatively from 5 to 10), andoptionally a T₇₅-T₂₅ of 25 to 45° C.

In at least one embodiment of the present invention when:

1) the unbridged group 4 metallocene compound (A) is run under the samepolymerization conditions as a supported two catalyst compositiondescribed herein, except that the unbridged metallocene compound (B) isabsent, a polymer having an RCI,m of 20 or more is produced; and2) the unbridged metallocene compound (B) is run under the samepolymerization conditions as step 1), except that the unbridged group 4metallocene compound (A) is absent, a polymer having an RCI,m of lessthan zero is produced.

In at least one embodiment of the present disclosure, a linear lowdensity polyethylene may be produced by using the supported catalystsystems (C′) described herein (e.g., having activator and two catalysts(A) and (B) supported on the same support) where the LLDPE has: a) anRCI,m greater than 30 (alternatively greater than 30 to 50), an Mw/Mn ofgreater than 3 to less than 5, and optionally a T₇₅-T₂₅ of 15-20° C.; orb) an RCI,m greater than 50 (alternatively greater than 80) and an Mw/Mnof greater than 5 (optionally of greater than 5 to 10), and optionally aT₇₅-T₂₅ of 25-45° C., provided that:

1) when the supported unbridged group 4 metallocene catalyst compound(A) is run under the same polymerization conditions as the supportedcatalyst system (C′) except that the unbridged metallocene catalystcompound (B) is absent, an ethylene polymer is produced having an RCI,mgreater than 20; and2) when the supported unbridged metallocene catalyst compound (B) is rununder the same conditions as step 1) except that the bridged group 4metallocene catalyst compound (A) is absent, an ethylene polymer isproduced having a negative RCI,m.

To obtain polymers having higher RCI,m's (such as 50 and above) selectunbridged catalyst compounds represented by formula (A) that producehigh comonomer content and/or high Mw/Mn.

End Uses

The multi-modal polyolefin produced by the processes disclosed hereinand blends thereof are useful in such forming operations as film, sheet,and fiber extrusion and co-extrusion as well as blow molding, injectionmolding, and rotary molding. Films include blown or cast films formed byco-extrusion or by lamination useful as shrink film, cling film, stretchfilm, sealing films, oriented films, snack packaging, heavy duty bags,grocery sacks, baked and frozen food packaging, medical packaging,industrial liners, membranes, etc., in food-contact and non-food contactapplications. Fibers include melt spinning, solution spinning and meltblown fiber operations for use in woven or non-woven form to makefilters, diaper fabrics, medical garments, geotextiles, etc. Extrudedarticles include medical tubing, wire and cable coatings, pipe,geomembranes, and pond liners. Molded articles include single andmulti-layered constructions in the form of bottles, tanks, large hollowarticles, rigid food containers and toys, etc.

Specifically, any of the foregoing polymers, such as the foregoingethylene copolymers or blends thereof, may be used in mono- ormulti-layer blown, extruded, and/or shrink films. These films may beformed by any number of well-known extrusion or coextrusion techniques,such as a blown bubble film processing technique, wherein thecomposition can be extruded in a molten state through an annular die andthen expanded to form a uni-axial or biaxial orientation melt prior tobeing cooled to form a tubular, blown film, which can then be axiallyslit and unfolded to form a flat film. Films may be subsequentlyunoriented, uniaxially oriented, or biaxially oriented to the same ordifferent extents.

Blends

The polymers produced herein may be further blended with additionalethylene polymers (referred to as “second ethylene polymers” or “secondethylene copolymers”) and use in film, molded part and other typicalpolyethylene applications.

In one aspect of the present disclosure, the second ethylene polymer isselected from ethylene homopolymer, ethylene copolymers, and blendsthereof. Useful second ethylene copolymers can comprise one or morecomonomers in addition to ethylene and can be a random copolymer, astatistical copolymer, a block copolymer, and/or blends thereof. Themethod of making the second ethylene polymer is not critical, as it canbe made by slurry, solution, gas phase, high pressure or other suitableprocesses, and by using catalyst systems appropriate for thepolymerization of polyethylenes, such as Ziegler-Natta-type catalysts,chromium catalysts, metallocene-type catalysts, other appropriatecatalyst systems or combinations thereof, or by free-radicalpolymerization. In a preferred embodiment, the second ethylene polymersare made by the catalysts, activators and processes described in U.S.Pat. Nos. 6,342,566; 6,384,142; 5,741,563; PCT Publication Nos. WO03/040201; and WO 97/19991. Such catalysts are well known in the art,and are described in, for example, ZIEGLER CATALYSTS (Gerhard Fink, RolfMülhaupt and Hans H. Brintzinger, eds., Springer-Verlag 1995); Resconiet al.; and I, II METALLOCENE-BASED POLYOLEFINS (Wiley & Sons 2000).Additional useful second ethylene polymers and copolymers are describedat paragraph [00118] to [00126] at pages 30 to 34 of PCT/US2016/028271,filed Apr. 19, 2016.

EXPERIMENTAL

Test Methods

¹H NMR

¹H NMR data was collected at 120° C. using a 10 mm CryoProbe with aBruker spectrometer at a ¹H frequency of 400 MHz (available from BrukerCorporation, United Kingdom). Data were recorded using a maximum pulsewidth of 45°, 5 seconds between pulses and signal averaging 512transients. Samples were prepared by dissolving 80 mg of sample in 3 mLof solvent heated at 140° C. Peak assignments are determined referencingthe solvent of tetrachloroethane-1,2 D₂ at 5.98 ppm.

GPC 4D Procedure

Unless otherwise indicated, the distributions and the moments ofmolecular weight (Mw, Mn, Mz, Mw/Mn, etc.), the comonomer content (C₂,C₃, C₆, etc.) and the branching index (g′) are determined by using ahigh temperature Gel Permeation Chromatography (Polymer Char GPC-IR)equipped with a multiple-channel band-filter based Infrared detectorIR5, an 18-angle light scattering detector and a viscometer. ThreeAgilent PLgel 10-μm Mixed-B LS columns are used to provide polymerseparation. Aldrich reagent grade 1,2,4-trichlorobenzene (TCB) with 300ppm antioxidant butylated hydroxytoluene (BHT) is used as the mobilephase. The TCB mixture is filtered through a 0.1-μm Teflon filter anddegassed with an online degasser before entering the GPC instrument. Thenominal flow rate is 1.0 ml/min and the nominal injection volume is 200μL. The whole system including transfer lines, columns, and detectorsare contained in an oven maintained at 145° C. Given amount of polymersample is weighed and sealed in a standard vial with 80-μL flow marker(Heptane) added to it. After loading the vial in the autosampler,polymer is automatically dissolved in the instrument with 8 ml added TCBsolvent. The polymer is dissolved at 160° C. with continuous shaking forabout 1 hour for most polyethylene samples or 2 hours for polypropylenesamples. The TCB densities used in concentration calculation are 1.463g/ml at room temperature and 1.284 g/ml at 145° C. The sample solutionconcentration is from 0.2 to 2.0 mg/ml, with lower concentrations beingused for higher molecular weight samples. The concentration (c), at eachpoint in the chromatogram is calculated from the baseline-subtracted IR5broadband signal intensity (I), using the following equation: c=βI,where β is the mass constant. The mass recovery is calculated from theratio of the integrated area of the concentration chromatography overelution volume and the injection mass which is equal to thepre-determined concentration multiplied by injection loop volume. Theconventional molecular weight (IR MW) is determined by combininguniversal calibration relationship with the column calibration which isperformed with a series of monodispersed polystyrene (PS) standardsranging from 700 to 10M gm/mole. The MW at each elution volume iscalculated with the following equation:

${\log\mspace{14mu} M} = {\frac{\log( {K_{PS}/K} )}{\alpha + 1} + {\frac{\alpha_{PS} + 1}{\alpha + 1}\log\mspace{14mu} M_{PS}}}$where the variables with subscript “PS” stand for polystyrene whilethose without a subscript are for the test samples. In this method,α_(PS)=0.67 and K_(PS)=0.000175, while α and K for other materials areas calculated and published in literature (Sun, T. et al.Macromolecules, 2001, 34, 6812), except that for purposes of the presentinvention, α=0.695 and K=0.000579 for linear ethylene polymers, α=0.705and K=0.0002288 for linear propylene polymers, α=0.695 and K=0.000181for linear butene polymers, α is 0.695 and K is0.000579*(1-0.0087*w2b+0.000018*(w2b){circumflex over ( )}) forethylene-butene copolymer where w2b is a bulk weight percent of butenecomonomer, α is 0.695 and K is 0.000579*(1-0.0075*w2b) forethylene-hexene copolymer where w2b is a bulk weight percent of hexenecomonomer, and α is 0.695 and K is 0.000579*(1-0.0077*w2b) forethylene-octene copolymer where w2b is a bulk weight percent of octenecomonomer. Concentrations are expressed in g/cm³, molecular weight isexpressed in g/mole, and intrinsic viscosity (hence K in theMark-Houwink equation) is expressed in dL/g unless otherwise noted.

The comonomer composition is determined by the ratio of the IR5 detectorintensity corresponding to CH₂ and CH₃ channel calibrated with a seriesof PE and PP homo/copolymer standards whose nominal values arepredetermined by NMR or FTIR. In particular, this provides the methylsper 1000 total carbons (CH₃/1000TC) as a function of molecular weight.The short-chain branch (SCB) content per 1000TC (SCB/1000TC) is thencomputed as a function of molecular weight by applying a chain-endcorrection to the CH₃/1000TC function, assuming each chain to be linearand terminated by a methyl group at each end. The weight % comonomer isthen obtained from the following expression in which f is 0.3, 0.4, 0.6,0.8, and so on for C₃, C₄, C₆, C₈, and so on co-monomers, respectively:w2=f*SCB/1000TC.

The bulk composition of the polymer from the GPC-IR and GPC-4D analysesis obtained by considering the entire signals of the CH₃ and CH₂channels between the integration limits of the concentrationchromatogram. First, the following ratio is obtained

${{Bulk}\mspace{14mu}{IR}\mspace{14mu}{ratio}} = {\frac{{Area}\mspace{14mu}{of}\mspace{14mu}{CH}_{3}\mspace{14mu}{signal}\mspace{14mu}{within}\mspace{14mu}{integration}\mspace{14mu}{limits}}{{Area}\mspace{14mu}{of}\mspace{14mu}{CH}_{2}\mspace{14mu}{signal}\mspace{14mu}{within}\mspace{14mu}{integration}\mspace{14mu}{limits}}.}$

Then the same calibration of the CH₃ and CH₂ signal ratio, as mentionedpreviously in obtaining the CH3/1000TC as a function of molecularweight, is applied to obtain the bulk CH₃/1000TC. A bulk methyl chainends per 1000TC (bulk CH₃end/1000TC) is obtained by weight-averaging thechain-end correction over the molecular-weight range. Thenw2b=f*bulk CH3/1000TCbulk SCB/1000TC=bulk CH3/1000TC−bulk CH3end/1000TCand bulk SCB/1000TC is converted to bulk w2 in the same manner asdescribed above.

The LS detector is the 18-angle Wyatt Technology High Temperature DAWNHELEOSII. The LS molecular weight (M) at each point in the chromatogramis determined by analyzing the LS output using the Zimm model for staticlight scattering (Light Scattering from Polymer Solutions; Huglin, M.B., Ed.; Academic Press, 1972.):

$\frac{K_{o}c}{\Delta\;{R(\theta)}} = {\frac{1}{{MP}(\theta)} + {2A_{2}{c.}}}$Here, ΔR(θ) is the measured excess Rayleigh scattering intensity atscattering angle θ, c is the polymer concentration determined from theIR5 analysis, A₂ is the second virial coefficient, P(θ) is the formfactor for a monodisperse random coil, and K_(O) is the optical constantfor the

$K_{o} = \frac{4\pi^{2}{n^{2}( {{{dn}/d}\; c} )}^{2}}{\lambda^{4}N_{A}}$where N_(A) is Avogadro's number, and (dn/dc) is the refractive indexincrement for the system. The refractive index, n=1.500 for TCB at 145°C. and λ=665 nm. For analyzing polyethylene homopolymers,ethylene-hexene copolymers, and ethylene-octene copolymers, dn/dc=0.1048ml/mg and A₂=0.0015; for analyzing ethylene-butene copolymers,dn/dc=0.1048*(1-0.00126*w2) ml/mg and A₂=0.0015 where w2 is weightpercent butene comonomer.

A high temperature Agilent (or Viscotek Corporation) viscometer, whichhas four capillaries arranged in a Wheatstone bridge configuration withtwo pressure transducers, is used to determine specific viscosity. Onetransducer measures the total pressure drop across the detector, and theother, positioned between the two sides of the bridge, measures adifferential pressure. The specific viscosity, η_(S), for the solutionflowing through the viscometer is calculated from their outputs. Theintrinsic viscosity, [η], at each point in the chromatogram iscalculated from the equation [η]=η_(S)/c, where c is concentration andis determined from the IR5 broadband channel output. The viscosity MW ateach point is calculated as M=K_(PS)M^(α) ^(PS) ⁺¹/[η], where α_(ps) is0.67 and K_(ps) is 0.000175.

The branching index (g′_(vis)) is calculated using the output of theGPC-IR5-LS-VIS method as follows. The average intrinsic viscosity,[η]_(avg), of the sample is calculated by:

$\lbrack\eta\rbrack_{avg} = \frac{\sum{c_{i}\lbrack\eta\rbrack}_{i}}{\sum c_{i}}$where the summations are over the chromatographic slices, i, between theintegration limits.

The branching index g′_(vis) is defined as

${g_{vis}^{\prime} = \frac{\lbrack\eta\rbrack_{avg}}{{KM}_{v}^{\alpha}}},$where M_(V) is the viscosity-average molecular weight based on molecularweights determined by LS analysis and the K and α are for the referencelinear polymer, which are, for purposes of the present invention,α=0.695 and K=0.000579 for linear ethylene polymers, α=0.705 andK=0.0002288 for linear propylene polymers, α=0.695 and K=0.000181 forlinear butene polymers, α is 0.695 and K is0.000579*(1-0.0087*w2b+0.000018*(w2b){circumflex over ( )}) forethylene-butene copolymer where w2b is a bulk weight percent of butenecomonomer, α is 0.695 and K is 0.000579*(1-0.0075*w2b) forethylene-hexene copolymer where w2b is a bulk weight percent of hexenecomonomer, and α is 0.695 and K is 0.000579*(1-0.0077*w2b) forethylene-octene copolymer where w2b is a bulk weight percent of octenecomonomer. Concentrations are expressed in g/cm³, molecular weight isexpressed in g/mole, and intrinsic viscosity (hence K in theMark-Houwink equation) is expressed in dL/g unless otherwise noted.Calculation of the w2b values is as discussed above.

The reversed-co-monomer index (RCI,m) is computed from x2 (mol %co-monomer C₃, C₄, C₆, C₈, etc.), as a function of molecular weight,where x2 is obtained from the following expression in which n is thenumber of carbon atoms in the comonomer (3 for C₃, 4 for C₄, 6 for C₆,etc.):

${x\; 2} = {- {\frac{200\mspace{14mu} w\; 2}{{{- 100}\mspace{14mu} n} - {2\mspace{14mu} w\; 2} + {{nw}\; 2}}.}}$

Then the molecular-weight distribution, W(z) where z=log₁₀ M, ismodified to W′(z) by setting to 0 the points in W that are less than 5%of the maximum of W; this is to effectively remove points for which theS/N in the composition signal is low. Also, points of W′ for molecularweights below 2000 gm/mole are set to 0. Then W′ is renormalized so that1=∫_(−∞) ^(∞) W′dzand a modified weight-average molecular weight (M_(w)′) is calculatedover the effectively reduced range of molecular weights as follows:M _(w)′=∫_(−∞) ^(∞)10^(z) *W′dz.

The RCI,m is then computed asRCI,m=∫ _(−∞) ^(∞) x2(10^(z) −M _(w)′)W′dz.

A reversed-co-monomer index (RCI,w) is also defined on the basis of theweight fraction co-monomer signal (w2/100) and is computed as follows:

${RCI},{w = {\int_{- \infty}^{\infty}{\frac{w\; 2}{100}( {10^{z} - M_{w}^{\prime}} )\ W^{\prime}{{dz}.}}}}$

Note that in the above definite integrals the limits of integration arethe widest possible for the sake of generality; however, in reality thefunction is only integrated over a finite range for which data isacquired, considering the function in the rest of the non-acquired rangeto be 0. Also, by the manner in which W′ is obtained, it is possiblethat W′ is a discontinuous function, and the above integrations need tobe done piecewise.

Three co-monomer distribution ratios are also defined on the basis ofthe % weight (w2) comonomer signal, denoted as CDR-1,w, CDR-2,w, andCDR-3,w, as follows:

${{CDR}\text{-}1},{w = \frac{w\; 2({Mz})}{w\; 2({Mw})}}$${{CDR}\text{-}2},{w = \frac{w\; 2({Mz})}{w\; 2( \frac{{Mw} + {Mn}}{2} )}}$${{CDR}\text{-}3},{w = \frac{w\; 2( \frac{{Mz} + {Mw}}{2} )}{w\; 2( \frac{{Mw} + {Mn}}{2} )}}$where w2(Mw) is the % weight co-monomer signal corresponding to amolecular weight of Mw, w2(Mz) is the % weight co-monomer signalcorresponding to a molecular weight of Mz, w2[(Mw+Mn)/2)] is the %weight co-monomer signal corresponding to a molecular weight of(Mw+Mn)/2, and w2[(Mz+Mw)/2] is the % weight co-monomer signalcorresponding to a molecular weight of Mz+Mw/2, where Mw is theweight-average molecular weight, Mn is the number-average molecularweight, and Mz is the z-average molecular weight.

Accordingly, the co-monomer distribution ratios can be also definedutilizing the % mole co-monomer signal, CDR-1,m, CDR-2,m, CDR-3,m, as

${{CDR}\text{-}1},{m = \frac{x\; 2({Mz})}{x\; 2({Mw})}}$${{CDR}\text{-}2},{m = \frac{x\; 2({Mz})}{x\; 2( \frac{{Mw} + {Mn}}{2} )}}$${{CDR}\text{-}3},{m = \frac{x\; 2( \frac{{Mz} + {Mw}}{2} )}{x\; 2( \frac{{Mw} + {Mn}}{2} )}}$where x2(Mw) is the % mole co-monomer signal corresponding to amolecular weight of Mw, x2(Mz) is the % mole co-monomer signalcorresponding to a molecular weight of Mz, x2[(Mw+Mn)/2)] is the % moleco-monomer signal corresponding to a molecular weight of (Mw+Mn)/2, andx2[(Mz+Mw)/2] is the % mole co-monomer signal corresponding to amolecular weight of Mz+Mw/2, where Mw is the weight-average molecularweight, Mn is the number-average molecular weight, and Mz is thez-average molecular weight.

All molecular weights are weight average (M_(w)) unless otherwise noted.All molecular weights are reported in g/mol unless otherwise noted.

Melt index (MI) also referred to as 12, reported in g/10 min, isdetermined according to ASTM D1238, 190° C., 2.16 kg load.

High load melt index (HLMI) also referred to as 121, reported in g/10min, is determined according to ASTM D1238, 190° C., 21.6 kg load.

Melt index ratio (MIR) is MI divided by HLMI as determined by ASTMD1238.

Room temperature is 23° C. unless otherwise indicated.

Density is determined according to ASTM 1505.

Catalyst Compounds

Polymerizations

All reactions were performed in an inert N₂ purged glove box unlessotherwise stated. All anhydrous solvents were purchased from FisherChemical and were degassed and dried over molecular sieves prior to use.Deuterated solvents were purchased from Cambridge Isotope Laboratoriesand dried over molecular sieves prior to use. n-Butyl lithium (2.5 Msolution in hexane), dicyclopentadiene, dimethyl sulfide (Me₂S) andtributyltin chloride (Bu₃SnCl) were purchased from Sigma-Aldrich.Hafnium tetrachloride (HfCl₄) 99+%, and trimethylsilylmethyltrifluoromethanesulfonate were purchased from Strem Chemicals and TCIAmerica respectively, and used as received.(Cyclopentadienyl)trichlorohafnium dimethoxyethane (CpHfCl₃(dme))¹,potassium cyclopentadienide (KCp)² and tributyltin cyclopentadienyl(Bu₃SnCp)³ were prepared according to the literature methods. The ¹H NMRmeasurements were recorded on a 400 MHz Bruker spectrometer.

Synthesis of trimethylsilylmethyl cyclopentadiene, Me₃SiCH₂CpH

A neat trimethylsilylmethyl trifluoromethanesulfonate (25.0 g, 105.8mmol) was dissolved in 300 mL of diethyl ether and cooled to −25° C.; tothis a solid potassium cyclopentadienide (11.14 g, 106.9 mmol) wasslowly added over a period of 10-15 minutes. The resulting mixture wasstirred overnight at room temperature. Insoluble materials were filteredout. Volatiles from the reaction mixture were carefully removed underdynamic vacuum to avoid evaporating the volatile trimethylsilylmethylcyclopentadiene, Me₃SiCH₂CpH. The reaction flask (250 mL round bottomflask) and frit with celite were weighted to calculate yield of theproduct after extraction. The crude materials were then extracted intopentane (3×50 mL) and used without any further purification. Based onabove mathematical method, the yield is calculated as 15.47 g (95.2%).The ¹H NMR spectrum was recorded for the crude material to ensure theproduct formation. ¹H NMR (400 MHz, C₆D₆): δ-0.05 (9H, s, Si—CH₃), 1.77(2H, d, J_(HH)=1.2 Hz, Me₃Si—CH₂), 2.83 (1H, sex, J_(HH)=1.5 Hz, Cp-CH),5.80-6.49 (4H, m, Cp-CH) ppm.

Synthesis of lithium trimethylsilylmethyl cyclopentadienide,Me₃SiCH₂CpLi

A hexane solution of n-butyl lithium (41.5 mL, 103.8 mmol, 2.5 Msolution) was added drop wise to a precooled solution (1:1 mixture ofpentane and diethyl ether, 200 mL) of Me₃SiCH₂CpH (15.47 g, 101.7 mmol)over a period of 40-50 minutes at −25° C. The resulting mixture wasgradually brought to room temperature and then continuously stirredovernight. Volatiles were removed in vacuo and remaining crude materialswere thoroughly washed with pentane. The final materials were driedunder vacuum to obtain a colorless crystalline solid of Me₃SiCH₂CpLi in13.6 g (84.6%) yield. ¹H NMR (400 MHz, THF-d₈): δ-0.09 (9H, s, Si—CH₃),1.84 (2H, s, Me₃Si—CH₂), 5.36 (2H, t, J_(HH)=2.6 Hz, Cp-CH), 5.47 (2H,t, J_(HH)=2.6 Hz, Cp-CH) ppm.

Synthesis of (Cyclopentadienyl)(trimethylsilylmethylcyclopentadienyl)hafnium dichloride, (Cp)(Me₃SiCH₂Cp)HfCl₂

A solid (cyclopentadienyl)trichlorohafnium dimethoxyethane (5.0 g, 11.36mmol) was slurried in 100 mL of precooled diethyl ether, and to this asolid Me₃SiCH₂CpLi (1.80 g, 11.36 mmol) was added over a period of 3-5minutes. The resulting mixture was stirred overnight at roomtemperature. All volatiles were removed in vacuo and the crude materialswere subsequently extracted into dichloromethane. Solvents were removedunder reduced pressure and then thoroughly washed with cold hexane toget rid of organic soluble impurities. Spectroscopically pure materialof (Cp)(Me₃SiCH₂Cp)HfCl₂ was obtained as a pale yellow solid in 5.2 g(98.1%) yield. ¹H NMR (400 MHz, CD₂Cl₂): δ-0.03 (9H, s, SiMe₃-CH₃), 2.09(2H, s, Me₃Si—CH₂), 5.89 (2H, t, J_(HH)=2.6 Hz, Cp-CH), 6.20 (2H, t,J_(HH)=2.6 Hz, Cp-CH), 6.36 (5H, s, Cp-CH) ppm.

Synthesis of (Cyclopentadienyl)(trimethylsilylmethylcyclopentadienyl)hafnium dimethyl, (Cp)(Me₃SiCH₂Cp)HfMe₂

An ethereal solution of MeLi (14.1 mL, 22.6 mmol) was added drop wise toa precooled diethyl ether solution of (Cp)(Me₃SiCH₂Cp)HfCl₂ (5.2 g, 11.2mmol) over a period of 10-15 minutes at −25° C. The resulting mixturewas stirred overnight at room temperature to ensure completion of thereaction. Insoluble materials were filtered through a pad of celite.Volatiles from the filtrate were removed under vacuum. The crudematerials were triturated with pentane and then extracted into pentane,followed by solvent removal afforded a colorless crystalline material of(Cp)(Me₃SiCH₂Cp)HfMe₂ in 4.7 g (98.7%) yield. ¹H NMR (400 MHz, C₆D₆):δ-0.27 (6H, s, Hf—CH₃), −0.01 (9H, s, SiMe₃-CH3), 1.79 (2H, s,Me₃Si—CH₂), 5.44-5.39 (4H, m, Cp-CH), 5.73 (5H, s, Cp-CH) ppm.

Synthesis of Bis-(trimethylsilylmethyl cyclopentadienide)hafniumdichloride, (Me₃SiCH₂Cp)₂HfCl₂

A solid HfCl₄ (1.011 g, 3.16 mmol) was slurried in precooled diethylether (30 mL) at −25° C., and to this a solid Me₃SiCH₂CpLi (1.0 g, 6.3mmol) was added over a period of 3-5 minutes. The resulting mixture wasstirred overnight at room temperature. All volatiles were removed invacuo and the crude materials were subsequently extracted intodichloromethane. Solvents were removed under reduced pressure resultedspectroscopically pure (Me₃SiCH₂Cp)₂HfCl₂ as a colorless solid in 1.13 g(70%) yield. ¹H NMR (400 MHz C₆D₆): δ-0.11 (18H, s, SiMe₃-CH₃), 2.18(4H, s, Me₃Si—CH₂), 5.68 (8H, s, Cp-CH) ppm.

Synthesis of Bis-(trimethylsilylmethyl cyclopentadienyl)hafniumdimethyl, (Me₃SiCH₂Cp)₂HfMe₂

An ethereal solution of MeLi (2.56 mL, 4.1 mmol) was added drop wise toa precooled diethyl ether solution of (Me₃SiCH₂Cp)₂HfCl₂ (1.12 g, 2.03mmol) over a period of 3-5 minutes at −25° C. The resulting mixture wasstirred overnight at room temperature to ensure completion of thereaction. Insoluble materials were filtered through a pad of celite.Volatiles from the filtrate were removed under vacuum. The crudematerials were triturated with pentane and then extracted into pentane,followed by solvent removal afforded a colorless crystalline material of(Me₃SiCH₂Cp)₂HfMe₂ in 875 mg (84.2%) yield. ¹H NMR (400 MHz, C₆D₆):δ-0.23 (6H, s, Hf—CH₃), 0.02 (18H, s, SiMe₃-CH3), 1.89 (4H, s,Me₃Si—CH₂), 5.54-5.48 (8H, m, Cp-CH) ppm.

Supported Catalyst Syntheses

ES-70 875C SMAO is methylalumoxane supported on silica ES-70 (PQCorporation, Conshohocken, Pa.) that has been calcined at 875° C. andwas prepared as follows.

In a 4 L stirred vessel in the drybox methylaluminoxane (MAO) (30 wt %in toluene) is added along with 2400 g of toluene. This solution is thenstirred at 60 RPM for 5 minutes. ES-70 silica that has been calcined at875° C. was then added to the vessel. This slurry is heated at 100° C.and stirred at 120 RPM for 3 hours. The temperature was then lowered andthe mixture was allowed to cool to ambient temperature over 2 hours. Thestirrer was then set to 8 RPM and placed under vacuum for 72 hours.After emptying the vessel and sieving the supported MAO, 1014 g wasobtained.

Supported Catalyst Pair A

(Bis(trimethylsilylmethyl-cyclopentadienide)hafnium(IV)dimethyl):(bis(1-methylindenyl)zirconium(IV) dimethyl)

A 1.0 g amount of prepared ES-70 875C SMAO was stirred in 10 mL oftoluene using a Celstir™ flask.Bis(trimethylsilylmethyl-cyclopentadienide)hafnium(IV) dimethyl (16.3mg, 32 μmol) and bis(1-methylindenyl)zirconium(IV) dimethyl (3.0 mg, 8μmol) were added to the slurry and stirred for three hours. The mixturewas filtered, washed with several 10 mL portions of hexane and thendried under vacuum, yielding 0.86 g of light yellow silica.

Supported Catalyst Pair B

(Trimethylsilylmethylcyclopentadienide(cyclopentadienide)hafnium(IV)dimethyl):(bis(1-methylindenyl)zirconium(IV) dimethyl); Ratio: 6:1

A 1.0 g amount of prepared ES-70 875C SMAO was stirred in 10 mL oftoluene using a Celstir™ flask.Trimethylsilylmethylcyclopentadienide(cyclopentadienide)hafnium(IV)dimethyl (14.4 mg, 34.4 μmol) and bis(1-methylindenyl)zirconium(IV)dimethyl (2.2 mg, 5.6 mol) were added to the slurry and stirred forthree hours. The mixture was filtered, washed with several 10 mLportions of hexane and then dried under vacuum, yielding 0.90 g ofoff-white silica.

Supported Catalyst Pair C

(Bis-trimethylsilylmethylcyclopentadienide hafnium (IV)dimethyl):(bis-ethylindenyl zirconium (IV) dimethyl); Ratio: 4:1

To a stirred vessel 1400 g of toluene was added along with 925 g ofmethylaluminoxane (30 wt % in toluene). To this solution 734 g of ES 70silica, available from PQ Corporation (calcined at 875° C.) was added.The mixture was stirred for three hours at 100° C. after which thetemperature was reduced and the reaction was allowed to cool to ambienttemperature.

Bis-trimethylsilylmethylcyclopentadienide hafnium (IV) dimethyl (16.35g, 32.00 mmol) and bis-ethylindenyl zirconium (IV) dimethyl (3.26 g,8.00 mmol) were then dissolved in toluene (250 g) and added to thevessel, which was stirred for two more hours. The mixing speed was thenreduced and stirred slowly while drying under vacuum for 60 hours, afterwhich 1038 g of light yellow silica was obtained.

Polymerization with Organosilica Support Catalyst Systems

A 2 L autoclave was heated to 110° C. and purged with N₂ for at least 30minutes. It was charged with dry NaCl (350 g; Fisher, S271-10 dehydratedat 180° C. and subjected to several pump/purge cycles and finally passedthrough a 16 mesh screen prior to use) and ES-70 875C SMAO (5 g) at 105°C. and stirred for 30 minutes. The temperature was adjusted to 85° C. Ata pressure of 2 psig N₂, dry, degassed 1-hexene (2.0 mL) was added tothe reactor with a syringe then the reactor was charged with N₂ to apressure of 20 psig. A mixture of H₂ and N₂ was flowed into reactor (120SCCM; 10% H₂ in N₂) while stirring the bed.

Catalysts indicated in Table 1 were injected into the reactor withethylene at a pressure of 220 psig; ethylene flow was allowed over thecourse of the run to maintain constant pressure in the reactor. 1-hexenewas fed into the reactor as a ratio to ethylene flow (0.1 g/g). Hydrogenwas fed to the reactor as a ratio to ethylene flow (0.5 mg/g). Thehydrogen and ethylene ratios were measured by on-line GC analysis.Polymerizations were halted after 1 hour by venting the reactor, coolingto room temperature then exposing to air. The salt was removed bywashing with water two times; the polymer was isolated by filtration,briefly washed with acetone and dried in air for at least two days.

TABLE 1 Gas Phase Polymerization of Ethylene and 1-Hexene Activity MI MwMn Mz Mw/ Mz/ Hexene gP/gsup. CDR- Supported Catalyst dg/min MIR g/molg/mol g/mol Mn Mw wt % Cat. g′(vis) RCI, m 2 m bis-(nPrCp)HfMe₂ 1.23 18102,605 34,368 179,343 2.99 1.75 11.1 8000 0.984 52.0 1.23 SupportedCatalyst 0.466 26 147,198 24,000 544,487 6.13 3.70 8.78 4364 0.941 188.31.97 Pair B Supported Catalyst 1.4 36 85,570 22,393 172,891 3.82 2.029.91 10752 0.950 52.4 1.29 Pair AGas Phase Pilot Run for Supported Catalyst Pair C

Polymerization was performed in an 18.5 foot tall gas-phase fluidizedbed reactor with a 10 foot body and an 8.5 foot expanded section. Cycleand feed gases were fed into the reactor body through a perforateddistributor plate, and the reactor was controlled at 300 psi and 70 mol% ethylene. The reactor temperature was maintained at 185° F. throughoutthe polymerization by controlling the temperature of the cycle gas loop.Hydrogen was lowered and hexene was roughly the same compared to astandard bis-(nPrCp)HfMe₂ catalyst. This indicates that the supportedcatalyst pair C had less overall molecular weight capability than thestandard, but a similar level of comonomer incorporation. Theseresponses could be varied by adjusting the ratio of the two catalystpairs. Roughly a 65% increase in activity was also observed for thesupported catalyst pair C compared to the (nPr)HfMe₂ catalyst.

TABLE 2 Gas Phase Pilot Run for Supported Catalyst Pair C Data PointCatalyst (nPr)HfMe₂ Cat Pair C Process Data H₂ conc. (molppm) 348 250Hydrogen flow (mlb/hr) 2.96 4.21 C₆/C₂ Ratio (mol %/mol %) 0.013 0.014Comonomer conc. (mol %) 0.90 0.95 C₂ conc. (mol %) 70 70 Comonomer/C₂Flow Ratio 0.079 0.080 C₂ flow (lb/hr) 107 117 H₂/C₂ Ratio (ppm/mol %)5.0 3.6 Rx. Pressure (psig) 300 300 Reactor Temp (F) 185 185 Avg.Bedweight (lb) 322 383 Production (lb/hr) 70 72 Residence Time (hr) 4.65.3 Avg Velocity (ft/s) 2.25 2.25 Catalyst Feed (g/hr) 5.015 3.111 CatActivity (g poly/g cat) 6314 10477 Product Data Melt Index (MI) dg/min1.04 0.98 HLMI dg/min 23.32 22.56 HLMI/MI Ratio 22.43 22.96 Density g/cc0.9180 0.9178

Overall, catalyst systems of the present invention can provide increasedactivity or enhanced polymer properties, to increase conversion orcomonomer incorporation, or to alter comonomer distribution. Catalystsystems and processes of the present invention can also provide ethylenepolymers having the unique properties of high stiffness, high toughnessand good processability.

All documents described herein are incorporated by reference herein,including any priority documents and/or testing procedures to the extentthey are not inconsistent with this text. As is apparent from theforegoing general description and the specific embodiments, while formsof the embodiments have been illustrated and described, variousmodifications can be made without departing from the spirit and scope ofthe present disclosure. Accordingly, it is not intended that the presentdisclosure be limited thereby. Likewise, the term “comprising” isconsidered synonymous with the term “including.” Likewise whenever acomposition, an element or a group of elements is preceded with thetransitional phrase “comprising,” it is understood that we alsocontemplate the same composition or group of elements with transitionalphrases “consisting essentially of,” “consisting of,” “selected from thegroup of consisting of.”

What is claimed is:
 1. A supported catalyst system comprising: anunbridged hafnium metallocene compound; an unbridged zirconiummetallocene compound; a support material; and an activator; wherein theunbridged hafnium metallocene compound is represented by formula (A):

where: M* is Hf; each of R¹, R², R⁴, and R⁵ is independently hydrogen,alkoxide, or C₁ to C₄₀ substituted or unsubstituted hydrocarbyl; R³ isindependently hydrogen, alkoxide, C₁ to C₄₀ substituted or unsubstitutedhydrocarbyl, or —R¹¹—SiR′₃ or —R¹¹—CR′₃ where R¹¹ is a C₁ to C₄hydrocarbyl, and each R′ is independently C₁ to C₂₀ substituted orunsubstituted hydrocarbyl; each R⁶, R⁷, R⁸, and R¹⁰ is independentlyhydrogen, halide, alkoxide, or C₁ to C₄₀ substituted or unsubstitutedhydrocarbyl; R⁹ is —CH₂—SiMe₃, —CH₂—SiEt₃, —CH₂—SiPr₃, —CH₂—SiBu₃,—CH₂—SiCy₃, —CH₂—SiH(CH₃)₂, —CH₂SiPh₃, —CH₂—Si(CH₃)₂Ph, —CH₂—Si(CH₃)Ph₂,—CH₂—Si(Et)₂Ph, —CH₂—Si(Et)Ph₂, —CH₂—Si(CH₂)₃Ph, —CH₂—Si(CH₂)₄Ph,—CH₂—Si(Cy)Ph₂, —CH₂—Si(Cy)₂Ph; —CH₂—Si(CH₃)₂Cy, or —CH₂—Si(CH₃)Cy₂;each X is independently a univalent anionic ligand, or two Xs are joinedto form a metallocyclic ring, or two Xs are joined to form a chelatingligand, a diene ligand, or an alkylidene ligand; and the unbridgedzirconium metallocene compound is represented by formula (B):Cp^(A)Cp^(B)ZrX′n  (B) wherein Cp^(A) is selected from the groupconsisting of cyclopentadienyl, substituted cyclopentadieny, indenyl,and substituted indenyl; Cp^(B) is substituted indenyl; each X′ isindependently a halide, a hydride, an alkyl group, an alkenyl group oran arylalkyl group; and n is 1 or
 2. 2. The supported catalyst system ofclaim 1, wherein M* of formula (A) is Hf, each R¹, R², R³, R⁴ and R⁵ isC₁ to C₂₀ alkyl.
 3. The supported catalyst system of claim 1, wherein R⁹is —CH₂—SiMe₃, —CH₂—SiEt₃, —CH₂—SiPr₃, —CH₂—SiBu₃, —CH₂—SiCy₃,—CH₂—SiH(CH₃)₂, —CH₂SiPh₃, —CH₂—Si(CH₃)₂Ph, —CH₂—Si(CH₃)Ph₂,—CH₂—Si(Et)₂Ph, —CH₂—Si(Et)Ph₂, —CH₂—Si(CH₂)₃Ph, —CH₂—Si(CH₂)₄Ph,—CH₂—Si(Cy)Ph₂, or —CH₂—Si(Cy)₂Ph.
 4. The supported catalyst system ofclaim 1, wherein the unbridged zirconium metallocene compound isselected from the group consisting of:rac/meso-bis(1-ethylindenyl)zirconium dimethyl,rac/meso-bis(1-methylindenyl)zirconium dichloride,rac/meso-bis(1-methylindenyl)zirconium dimethyl,rac/meso-bis(1-propylindenyl)zirconium dichloride,rac/meso-bis(1-propylindenyl)zirconium dimethyl,rac/meso-bis(1-butylindenyl)zirconium dichloride,rac/meso-bis(1-butylindenyl)zirconium dimethyl, meso-bis(1ethylindenyl)zirconium dichloride, meso-bis(1-ethylindenyl) zirconium dimethyl,(1-methylindenyl)(pentamethylcyclopentadienyl) zirconium dichloride, and(1-methylindenyl)(pentamethyl cyclopentadienyl) zirconium dimethyl, andthe alkyl or halide versions thereof where the dimethyl is replaced withBz₂, Et₂, Ph₂, Br₂, or I₂.
 5. The supported catalyst system of claim 1,wherein the support material has a surface area from 10 m²/g to 700 m²/gand an average particle diameter from 10 μm to 500 μm.
 6. The supportedcatalyst system of claim 1, wherein the support material is selectedfrom the group consisting of silica, alumina, silica-alumina, andcombinations thereof.
 7. The supported catalyst system of claim 1,wherein the support material is fluorided, or sulfated.
 8. The supportedcatalyst system of claim 7, wherein the support material has a fluorineconcentration in the range of 0.6 wt % to 3.5 wt %, based upon theweight of the support material.
 9. The supported catalyst system ofclaim 1, wherein the activator comprises alumoxane or a noncoordinatinganion.
 10. The supported catalyst system of claim 1, wherein theactivator is methylalumoxane.
 11. The supported catalyst system of claim1, wherein the support is a silica aluminate and is treated with anelectron withdrawing anion such as fluoride or sulphate.
 12. Thesupported catalyst system of claim 1, wherein the electron withdrawinganion treated supported is treated with an alkyl aluminum.
 13. Thesupported catalyst system of claim 1, wherein the electron withdrawinganion treated supported is treated with an alkyl aluminum and issubstantially free of methyl alumoxane or a noncoordinating anion. 14.The supported catalyst system of claim 1, wherein the unbridgedmetallocene compound represented by formula (B) is present in thecatalyst system as at least two isomers.
 15. The supported catalystsystem of claim 1, wherein the activator comprises one or more of:N,N-dimethylanilinium tetrakis(perfluoronaphthyl)borate,N,N-dimethylanilinium tetrakis(perfluorobiphenyl)borate,N,N-dimethylanilinium tetrakis(perfluorophenyl)borate,N,N-dimethylanilinium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,triphenylcarbenium tetrakis(perfluoronaphthyl)borate, triphenylcarbeniumtetrakis(perfluorobiphenyl)borate, triphenylcarbeniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triphenylcarbeniumtetrakis(perfluorophenyl)borate, [Me₃NH⁺][B(C₆F₅)⁴⁻],1-(4-(tris(pentafluorophenyl)borate)-2,3,5,6-tetrafluorophenyl)pyrrolidinium; [Me₃NH⁺][B(C₆F₅)⁴⁻],1-(4-(tris(pentafluorophenyl)borate)-2,3,5,6-tetrafluorophenyl)pyrrolidinium, sodium tetrakis(pentafluorophenyl)borate, potassiumtetrakis(pentafluorophenyl)borate,4-(tris(pentafluorophenyl)borate)-2,3,5,6-tetrafluoropyridinium,solidium tetrakis(perfluorophenyl)aluminate, potassiumterakis(pentafluorophenyl), and N,N-dimethylaniliniumtetrakis(perfluorophenyl)aluminate.
 16. A supported catalyst systemcomprising: an unbridged hafnium metallocene compound; an unbridgedzirconium metallocene compound; a support material; and an activator;wherein the unbridged zirconium metallocene compound is represented byformula (B):Cp^(A)Cp^(B)ZrX′n  (B) wherein Cp^(A) is selected from the groupconsisting of cyclopentadienyl, substituted cyclopentadieny, indenyl,and substituted indenyl, Cp^(B) is substituted indenyl, each X′ isindependently a halide, a hydride, an alkyl group, an alkenyl group oran arylalkyl group, and n is 1 or 2; and the unbridged hafniummetallocene compound is one or more of: (Cp)(3-CH₂—SiMe₃-Cp)HfMe₂;(MeCp)(3-CH₂—SiMe₃-Cp)HfMe₂; (EtCp)(3-CH₂—SiMe₃-Cp)HfMe₂;(PrCp)(3-CH₂—SiMe₃-Cp)HfMe₂; (BuCp)(3-CH₂—SiMe₃-Cp)HfMe₂;(BzCp)(3-CH₂—SiMe₃-Cp)HfMe₂; (3-CH₂—SiMe₃-Cp)₂HfMe₂;(Me₃Cp)(3-CH₂—SiMe₃-Cp)HfMe₂; (Me₄Cp)(3-CH₂—SiMe₃-Cp)HfMe₂;(Me₅Cp)(3-CH₂—SiMe₃-Cp)HfMe₂; (1-Me, 3-Bu-Cp)(3-CH₂—SiMe₃-Cp)HfMe₂;(1-Me, 3-Ph-Cp)(3-CH₂—SiMe₃-Cp)HfMe₂; (Me₄Cp-Pr)(3-CH₂—SiMe₃-Cp)HfMe₂;(Me₄Cp-CH₂—SiMe₃)(3-CH₂—SiMe₃-Cp)HfMe₂; (2-Me,3-CH₂—SiMe₃-Ind)₂HfMe₂;(2-Et,3-CH₂—SiMe₃-Ind)₂HfMe₂; (2-Pr,3-CH₂—SiMe₃-Ind)₂HfMe₂;(2-Bu,3-CH₂—SiMe₃-Ind)₂HfMe₂; (2-Ph,3-CH₂—SiMe₃-Ind)₂HfMe₂;(3-CH₂—SiMe₃-Ind)₂HfMe₂; (3-CH₂—SiMe₃-Ind)(3-CH₂—SiMe₃-Cp)HfMe₂;(3-Me-Ind)(3-CH₂—SiMe₃-Cp)HfMe₂; (3-Et-Ind)(3-CH₂—SiMe₃-Cp)HfMe₂;(3-Pr-Ind)(3-CH₂—SiMe₃-Cp)HfMe₂; (3-Bu-Ind)(3-CH₂—SiMe₃-Cp)HfMe₂;(Cp)(3-CH₂—SiMe₃-Ind)HfMe₂; (MeCp)(3-CH₂—SiMe₃-Ind)HfMe₂;(EtCp)(3-CH₂—SiMe₃-Ind)HfMe₂; (PrCp)(3-CH₂—SiMe₃-Ind)HfMe₂;(BuCp)(3-CH₂—SiMe₃-Ind)HfMe₂; (Me₃Cp)(3-CH₂—SiMe₃-Ind)HfMe₂;(Me₄Cp)(3-CH₂—SiMe₃-Ind)HfMe₂; (Me₅Cp)(3-CH₂—SiMe₃-Ind)HfMe₂; (1-Me,3-Bu-Cp)(3-CH₂—SiMe₃-Ind)HfMe₂; (1-Me, 3-Ph-Cp)(3-CH₂—SiMe₃-Ind)HfMe₂;(Cp)(3-CH₂—SiMe₃-Cp)HfMe₂; (MeCp)(3-CH₂—SiMe₃-Cp)HfMe₂;(EtCp)(3-CH₂—SiMe₃-Cp)HfMe₂; (PrCp)(3-CH₂—SiMe₃-Cp)HfMe₂;(BuCp)(3-CH₂—SiMe₃-Cp)HfMe₂; (BzCp)(3-CH₂—SiMe₃-Cp)HfMe₂;(3-CH₂—SiMe₃-Cp)₂HfMe₂; (Me₂Cp)(3-CH₂—SiMe₃-Cp)HfMe₂;(Me₃Cp)(3-CH₂—SiMe₃-Cp)HfMe₂; (Me₄Cp)(3-CH₂—SiMe₃-Cp)HfMe₂;(Me₅Cp)(3-CH₂—SiMe₃-Cp)HfMe₂; (Et₂Cp)(3-CH₂—SiMe₃-Cp)HfMe₂;(Et₃Cp)(3-CH₂—SiMe₃-Cp)HfMe₂; (Et₄Cp)(3-CH₂—SiMe₃-Cp)HfMe₂;(Et₅Cp)(3-CH₂—SiMe₃-Cp)HfMe₂; (Pr₂Cp)(3-CH₂—SiMe₃-Cp)HfMe₂;(Pr₃Cp)(3-CH₂—SiMe₃-Cp)HfMe₂; (Pr₄Cp)(3-CH₂—SiMe₃-Cp)HfMe₂;(Pr₅Cp)(3-CH₂—SiMe₃-Cp)HfMe₂; (Bu₂Cp)(3-CH₂—SiMe₃-Cp)HfMe₂;(Bu₃Cp)(3-CH₂—SiMe₃-Cp)HfMe₂; (Bu₄Cp)(3-CH₂—SiMe₃-Cp)HfMe₂;(Bu₅Cp)(3-CH₂—SiMe₃-Cp)HfMe₂; (Bz₂Cp)(3-CH₂—SiMe₃-Cp)HfMe₂;(Bz₃Cp)(3-CH₂—SiMe₃-Cp)HfMe₂; (Bz₄Cp)(3-CH₂—SiMe₃-Cp)HfMe₂;(Bz₅Cp)(3-CH₂—SiMe₃-Cp)HfMe₂; (EtMe₄Cp)(3-CH₂—SiMe₃-Cp)HfMe₂;(PrMe₄Cp)(3-CH₂—SiMe₃-Cp)HfMe₂; (BuMe₄Cp)(3-CH₂—SiMe₃-Cp)HfMe₂;(PnMe₄Cp)(3-CH₂—SiMe₃-Cp)HfMe₂; (HxMe₄Cp)(3-CH₂—SiMe₃-Cp)HfMe₂;(BzMe₄Cp)(3-CH₂—SiMe₃-Cp)HfMe₂; (Me₄Cp-CH₂—SiMe₃)(3-CH₂—SiMe₃-Cp)HfMe₂;(Me₄Cp-CH₂—SiMe₂Ph)(3-CH₂—SiMe₃-Cp)HfMe₂;(Me₄Cp-CH₂—SiMe₂Ph)(3-CH₂—SiMe₃-Cp)HfMe₂;(Me₄Cp-CH₂—SiMePh₂)(3-CH₂—SiMe₃-Cp)HfMe₂;(Me₄Cp-CH₂—SiPh₃)(3-CH₂—SiMe₃-Cp)HfMe₂;(Me₄Cp-CH₂—SiMe₂Cy)(3-CH₂—SiMe₃-Cp)HfMe₂;(Me₄Cp-CH₂—SiMeCy₂)(3-CH₂—SiMe₃-Cp)HfMe₂;(Me₄Cp-CH₂—SiCy₃)(3-CH₂—SiMe₃-Cp)HfMe₂; (EtMe₃Cp)(3-CH₂—SiMe₃-Cp)HfMe₂;(PrMe₃Cp)(3-CH₂—SiMe₃-Cp)HfMe₂; (BuMe₃Cp)(3-CH₂—SiMe₃-Cp)HfMe₂;(BzMe₃Cp)(3-CH₂—SiMe₃-Cp)HfMe₂; (Me₃Cp-CH₂—SiMe₃)(3-CH₂—SiMe₃-Cp)HfMe₂;(Me₃Cp-CH₂—SiMe₂Ph)(3-CH₂—SiPh₃-Cp)HfMe₂;(Me₃Cp-CH₂—SiMePh₂)(3-CH₂—SiMe₃-Cp)HfMe₂;(Me₃Cp-CH₂—SiPh₃)(3-CH₂—SiMe₃-Cp)HfMe₂;(Me₃Cp-CH₂—SiMe₂Cy)(3-CH₂—SiMe₃-Cp)HfMe₂;(Me₃Cp-CH₂—SiMeCy₂)(3—CH₂—SiMe₃-Cp)HfMe₂;(Me₃Cp-CH₂—SiCy₃)(3-CH₂—SiMe₃-Cp)HfMe₂; (MeEtCp)(3-CH₂—SiMe₃-Cp)HfMe₂;(MePrCp)(3-CH₂—SiMe₃-Cp)HfMe₂; (MeBuCp)(3-CH₂—SiMe₃-Cp)HfMe₂;(BzMeCp)(3-CH₂—SiMe₃-Cp)HfMe₂; (EtPrCp)(3-CH₂—SiMe₃-Cp)HfMe₂;(EtBuCp)(3-CH₂—SiMe₃-Cp)HfMe₂; (BzEtCp)(3-CH₂—SiMe₃-Cp)HfMe₂;(PrBuCp)(3-CH₂—SiMe₃-Cp)HfMe₂; (BzPrCp)(3-CH₂—SiMe₃-Cp)HfMe₂;(BuBzCp)(3-CH₂—SiMe₃-Cp)HfMe₂; (Cp)(3-CH₂—SiMe₂Ph-Cp)HfMe₂;(MeCp)(3-CH₂—SiMe₂Ph-Cp)HfMe₂; (EtCp)(3-CH₂—SiMe₂Ph-Cp)HfMe₂;(PrCp)(3-CH₂—SiMe₂Ph-Cp)HfMe₂; (BuCp)(3-CH₂—SiMe₂Ph-Cp)HfMe₂;(BzCp)(3-CH₂—SiMe₂Ph-Cp)HfMe₂; (3-CH₂—SiMe₂Ph-Cp)₂HfMe₂;(Me₂Cp)(3-CH₂—SiMe₂Ph-Cp)HfMe₂; (Me₃Cp)(3-CH₂—SiMe₂Ph-Cp)HfMe₂;(Me₄Cp)(3-CH₂—SiMe₂Ph-Cp)HfMe₂; (Me₅Cp)(3-CH₂—SiMe₂Ph-Cp)HfMe₂;(Et₂Cp)(3-CH₂—SiMe₂Ph-Cp)HfMe₂; (Et₃Cp)(3-CH₂—SiMe₂Ph-Cp)HfMe₂;(Et₄Cp)(3-CH₂—SiMe₂Ph-Cp)HfMe₂; (Et₅Cp)(3-CH₂—SiMe₂Ph-Cp)HfMe₂;(Pr₂Cp)(3-CH₂—SiMe₂Ph-Cp)HfMe₂; (Pr₃Cp)(3-CH₂—SiMe₂Ph-Cp)HfMe₂;(Pr₄Cp)(3-CH₂—SiMe₂Ph-Cp)HfMe₂; (Pr₅Cp)(3-CH₂—SiMe₂Ph-Cp)HfMe₂;(Bu₂Cp)(3-CH₂—SiMe₂Ph-Cp)HfMe₂; (Bu₃Cp)(3-CH₂—SiMe₂Ph-Cp)HfMe₂;(Bu₄Cp)(3-CH₂—SiMe₂Ph-Cp)HfMe₂; (Bu₅Cp)(3-CH₂—SiMe₂Ph-Cp)HfMe₂;(Bz₂Cp)(3-CH₂—SiMe₂Ph-Cp)HfMe₂; (Bz₃Cp)(3-CH₂—SiMe₂Ph-Cp)HfMe₂;(Bz₄Cp)(3-CH₂—SiMe₂Ph-Cp)HfMe₂; (Bz₅Cp)(3-CH₂—SiMe₂Ph-Cp)HfMe₂;(EtMe₄Cp)(3-CH₂—SiMe₂Ph-Cp)HfMe₂; (PrMe₄Cp)(3-CH₂—SiMe₂Ph-Cp)HfMe₂;(BuMe₄Cp)(3-CH₂—SiMe₂Ph-Cp)HfMe₂; (BzMe₄Cp)(3-CH₂—SiMe₂Ph-Cp)HfMe₂;(Me₄Cp-CH₂—SiMe₃)(3-CH₂—SiMe₂Ph-Cp)HfMe₂;(Me₄Cp-CH₂—SiMe₂Ph)(3-CH₂—SiMe₂Ph-Cp)HfMe₂;(Me₄Cp-CH₂—SiMePh₂)(3-CH₂—SiMe₂Ph-Cp)HfMe₂;(Me₄Cp-CH₂—SiPh₃)(3-CH₂—SiMe₂Ph-Cp)HfMe₂;(Me₄Cp-CH₂—SiMe₂Cy)(3-CH₂—SiMe₂Ph-Cp)HfCl₂;(Me₄Cp-CH₂—SiMeCy₂)(3-CH₂—SiMe₂Ph-Cp)HfCl₂;(Me₄Cp-CH₂—SiCy₃)(3-CH₂—SiMe₂Ph-Cp)HfMe₂;(EtMe₃Cp)(3-CH₂—SiMe₂Ph-Cp)HfMe₂; (PrMe₃Cp)(3-CH₂—SiMe₂Ph-Cp)HfMe₂;(BuMe₃Cp)(3-CH₂—SiMe₂Ph-Cp)HfMe₂; (BzMe₃Cp)(3-CH₂—SiMe₂Ph-Cp)HfMe₂;(Me₃Cp-CH₂—SiMe₃)(3-CH₂—SiMe₂Ph-Cp)HfMe₂;(Me₃Cp-CH₂—SiMe₂Ph)(3-CH₂—SiMe₂Ph-Cp)HfMe₂;(Me₃Cp-CH₂—SiMePh₂)(3-CH₂—SiMe₂Ph-Cp)HfMe₂;(Me₃Cp-CH₂—SiPh₃)(3-CH₂—SiMe₂Ph-Cp)HfMe₂;(Me₃Cp-CH₂—SiMe₂Cy)(3-CH₂—SiMe₂Ph-Cp)HfMe₂;(Me₃Cp-CH₂—SiMeCy₂)(3-CH₂—SiMe₂Ph-Cp)HfMe₂;(Me₃Cp-CH₂—SiCy₃)(3-CH₂—SiMe₂Ph-Cp)HfMe₂;(MeEtCp)(3-CH₂—SiMe₂Ph-Cp)HfMe₂; (MePrCp)(3-CH₂—SiMe₂Ph-Cp)HfMe₂;(MeBuCp)(3-CH₂—SiMe₂Ph-Cp)HfMe₂; (BzMeCp)(3-CH₂—SiMe₂Ph-Cp)HfMe₂;(EtPrCp)(3-CH₂—SiMe₂Ph-Cp)HfMe₂; (EtBuCp)(3-CH₂—SiMe₂Ph-Cp)HfMe₂;(BzEtCp)(3-CH₂—SiMe₂Ph-Cp)HfMe₂; (PrBuCp)(3-CH₂—SiMe₂Ph-Cp)HfMe₂;(BzPrCp)(3-CH₂—SiMe₂Ph-Cp)HfMe₂; (BuBzCp)(3-CH₂—SiMe₂Ph-Cp)HfMe₂;(Cp)(3-CH₂—SiMePh₂-Cp)HfMe₂; (MeCp)(3-CH₂—SiMePh₂-Cp)HfMe₂;(EtCp)(3-CH₂—SiMePh₂-Cp)HfMe₂; (PrCp)(3-CH₂—SiMePh₂-Cp)HfMe₂;(BuCp)(3-CH₂—SiMePh₂-Cp)HfMe₂; ((BzCp)(3-CH₂—SiMePh₂-Cp)HfMe₂;(3-CH₂—SiMePh₂-Cp)₂HfMe₂; (Me₂Cp)(3-CH₂—SiMePh₂-Cp)HfMe₂;(Me₃Cp)(3-CH₂—SiMePh₂-Cp)HfMe₂; (Me₄Cp)(3-CH₂—SiMePh₂-Cp)HfMe₂;(Me₅Cp)(3-CH₂—SiMePh₂-Cp)HfMe₂; (Et₂Cp)(3-CH₂—SiMePh₂-Cp)HfMe₂;(Et₃Cp)(3-CH₂—SiMePh₂-Cp)HfMe₂; (Et₄Cp)(3-CH₂—SiMePh₂-Cp)HfMe₂;(Et₅Cp)(3-CH₂—SiMePh₂-Cp)HfMe₂; (Pr₂Cp)(3-CH₂—SiMePh₂-Cp)HfMe₂;(Pr₃Cp)(3-CH₂—SiMePh₂-Cp)HfMe₂; (Pr₄Cp)(3-CH₂—SiMePh₂-Cp)HfMe₂;(Pr₅Cp)(3-CH₂—SiMePh₂-Cp)HfMe₂; (Bu₂Cp)(3-CH₂—SiMePh₂-Cp)HfMe₂;(Bu₃Cp)(3-CH₂—SiMePh₂-Cp)HfMe₂; (Bu₄Cp)(3-CH₂—SiMePh₂-Cp)HfMe₂;(Bu₅Cp)(3-CH₂—SiMePh₂-Cp)HfMe₂; (Bz₂Cp)(3-CH₂—SiMePh₂-Cp)HfMe₂;(Bz₃Cp)(3-CH₂—SiMePh₂-Cp)HfMe₂; (Bz₄Cp)(3-CH₂—SiMePh₂-Cp)HfMe₂;(Bz₅Cp)(3-CH₂—SiMePh₂-Cp)HfMe₂; (EtMe₄Cp)(3-CH₂—SiMePh₂-Cp)HfMe₂;(PrMe₄Cp)(3-CH₂—SiMePh₂-Cp)HfMe₂; (BuMe₄Cp)(3-CH₂—SiMePh₂-Cp)HfMe₂;(PnMe₄Cp)(3-CH₂—SiMePh₂-Cp)HfMe₂; (HxMe₄Cp)(3-CH₂—SiMePh₂-Cp)HfMe₂;(BzMe₄Cp)(3-CH₂—SiMePh₂-Cp)HfMe₂;(Me₄Cp-CH₂—SiMe₃)(3-CH₂—SiMePh₂-Cp)HfMe₂;(Me₄Cp-CH₂—SiMe₂Ph)(3-CH₂—SiMePh₂-Cp)HfMe₂;(Me₄Cp-CH₂—SiMePh₂)(3-CH₂—SiMePh₂-Cp)HfMe₂;(Me₄Cp-CH₂—SiPh₃)(3-CH₂—SiMePh₂-Cp)HfMe₂;(Me₄Cp-CH₂—SiMe₂Cy)(3-CH₂—SiMePh₂-Cp)HfMe₂;(Me₄Cp-CH₂—SiMeCy₂)(3-CH₂—SiMePh₂-Cp)HfMe₂;(Me₄Cp-CH₂—SiCy₃)(3-CH₂—SiMePh₂-Cp)HfMe₂;(EtMe₃Cp)(3-CH₂—SiMePh₂-Cp)HfMe₂; (PrMe₃Cp)(3-CH₂—SiMePh₂-Cp)HfMe₂;(BuMe₃Cp)(3-CH₂—SiMePh₂-Cp)HfMe₂; (BzMe₃Cp)(3-CH₂—SiMePh₂-Cp)HfMe₂;(Me₃Cp-CH₂—SiMe₃)(3-CH₂—SiMePh₂-Cp)HfMe₂;(Me₃Cp-CH₂—SiMe₂Ph)(3-CH₂—SiMePh₂-Cp)HfMe₂;(Me₃Cp-CH₂—SiMePh₂)(3-CH₂—SiMePh₂-Cp)HfMe₂;(Me₃Cp-CH₂—SiPh₃)(3-CH₂—SiMePh₂-Cp)HfMe₂;(Me₃Cp-CH₂—SiMe₂Cy)(3-CH₂—SiMePh₂-Cp)HfMe₂;(Me₃Cp-CH₂—SiMeCy₂)(3-CH₂—SiMePh₂-Cp)HfMe₂;(Me₃Cp-CH₂—SiCy₃)(3-CH₂—SiMePh₂-Cp)HfMe₂;(MeEtCp)(3-CH₂—SiMePh₂-Cp)HfMe₂; (MePrCp)(3-CH₂—SiMePh₂-Cp)HfMe₂;(MeBuCp)(3-CH₂—SiMePh₂-Cp)HfMe₂; (BzMeCp)(3-CH₂—SiMePh₂-Cp)HfMe₂;(EtPrCp)(3-CH₂—SiMePh₂-Cp)HfMe₂; (EtBuCp)(3-CH₂—SiMePh₂-Cp)HfMe₂;(BzEtCp)(3-CH₂—SiMePh₂-Cp)HfMe₂; (PrBuCp)(3-CH₂—SiMePh₂-Cp)HfMe₂;(BzPrCp)(3-CH₂—SiMePh₂-Cp)HfMe₂; (BuBzCp)(3-CH₂—SiMePh₂-Cp)HfMe₂;(Cp)(3-CH₂—SiPh₃-Cp)HfMe₂; (MeCp)(3-CH₂—SiPh₃-Cp)HfMe₂;(EtCp)(3-CH₂—SiPh₃-Cp)HfMe₂; (PrCp)(3-CH₂—SiPh₃-Cp)HfMe₂;(BuCp)(3-CH₂—SiPh₃-Cp)HfMe₂; (BzCp)(3-CH₂—SiPh₃-Cp)HfMe₂;(3-CH₂—SiPh₃-Cp)₂HfMe₂; (Me₂Cp)(3-CH₂—SiPh₃-Cp)HfMe₂;(Me₃Cp)(3-CH₂—SiPh₃-Cp)HfMe₂; (Me₄Cp)(3-CH₂—SiPh₃-Cp)HfMe₂;(Me₅Cp)(3-CH₂—SiPh₃-Cp)HfMe₂; (Et₂Cp)(3-CH₂—SiPh₃-Cp)HfMe₂;(Et₃Cp)(3-CH₂—SiPh₃-Cp)HfMe₂; (Et₄Cp)(3-CH₂—SiPh₃-Cp)HfMe₂;(Et₅Cp)(3-CH₂—SiPh₃-Cp)HfMe₂; (Pr₂Cp)(3-CH₂—SiPh₃-Cp)HfMe₂;(Pr₃Cp)(3-CH₂—SiPh₃-Cp)HfMe₂; (Pr₄Cp)(3-CH₂—SiPh₃-Cp)HfMe₂;(Pr₅Cp)(3-CH₂—SiPh₃-Cp)HfMe₂; (Bu₂Cp)(3-CH₂—SiPh₃-Cp)HfMe₂;(Bu₃Cp)(3-CH₂—SiPh₃-Cp)HfMe₂; (Bu₄Cp)(3-CH₂—SiPh₃-Cp)HfMe₂;(Bu₅Cp)(3-CH₂—SiPh₃-Cp)HfMe₂; (Bz₂Cp)(3-CH₂—SiPh₃-Cp)HfMe₂;(Bz₃Cp)(3-CH₂—SiPh₃-Cp)HfMe₂; (Bz₄Cp)(3-CH₂—SiPh₃-Cp)HfMe₂;(Bz₅Cp)(3-CH₂—SiPh₃-Cp)HfMe₂; (EtMe₄Cp)(3-CH₂—SiPh₃-Cp)HfMe₂;(PrMe₄Cp)(3-CH₂—SiPh₃-Cp)HfMe₂; (BuMe₄Cp)(3-CH₂—SiPh₃-Cp)HfMe₂;(BzMe₄Cp)(3-CH₂—SiPh₃-Cp)HfMe₂; (Me₄Cp-CH₂—SiMe₃)(3-CH₂—SiPh₃-Cp)HfMe₂;(Me₄Cp-CH₂—SiMe₂Ph)(3-CH₂—SiPh₃-Cp)HfMe₂;(Me₄Cp-CH₂—SiMePh₂)(3-CH₂—SiPh₃-Cp)HfMe₂;(Me₄Cp-CH₂—SiPh₃)(3-CH₂—SiPh₃-Cp)HfMe₂;(Me₄Cp-CH₂—SiMe₂Cy)(3-CH₂—SiPh₃-Cp)HfMe₂;(Me₄Cp-CH₂—SiMeCy₂)(3-CH₂—SiPh₃-Cp)HfMe₂;(Me₄Cp-CH₂—SiCy₃)(3-CH₂—SiPh₃-Cp)HfMe₂; (EtMe₃Cp)(3-CH₂—SiPh₃-Cp)HfMe₂;(PrMe₃Cp)(3-CH₂—SiPh₃-Cp)HfMe₂; (BuMe₃Cp)(3-CH₂—SiPh₃-Cp)HfMe₂;(BzMe₃Cp)(3-CH₂—SiPh₃-Cp)HfMe₂; (Me₃Cp-CH₂—SiMe₃)(3-CH₂—SiPh₃-Cp)HfMe₂;(Me₃Cp-CH₂—SiMe₂Ph)(3-CH₂—SiPh₃-Cp)HfMe₂;(Me₃Cp-CH₂—SiMePh₂)(3-CH₂—SiPh₃-Cp)HfMe₂;(Me₃Cp-CH₂—SiPh₃)(3-CH₂—SiPh₃-Cp)HfMe₂;(Me₃Cp-CH₂—SiMe₂Cy)(3-CH₂—SiPh₃-Cp)HfMe₂;(Me₃Cp-CH₂—SiMeCy₂)(3-CH₂—SiPh₃-Cp)HfMe₂;(Me₃Cp-CH₂—SiCy₃)(3-CH₂—SiPh₃-Cp)HfMe₂; (MeEtCp)(3-CH₂—SiPh₃-Cp)HfMe₂;(MePrCp)(3-CH₂—SiPh₃-Cp)HfMe₂; (MeBuCp)(3-CH₂—SiPh₃-Cp)HfMe₂;(BzMeCp)(3-CH₂—SiPh₃-Cp)HfMe₂; (EtPrCp)(3-CH₂—SiPh₃-Cp)HfMe₂;(EtBuCp)(3-CH₂—SiPh₃-Cp)HfMe₂; (BzEtCp)(3-CH₂—SiPh₃-Cp)HfMe₂;(PrBuCp)(3-CH₂—SiPh₃-Cp)HfMe₂; (BzPrCp)(3-CH₂—SiPh₃-Cp)HfMe₂;(BuBzCp)(3-CH₂—SiPh₃-Cp)HfMe₂; (Cp)(3-CH₂—SiCyMe₂-Cp)HfMe₂;(MeCp)(3-CH₂—SiCyMe₂-Cp)HfMe₂; (EtCp)(3-CH₂—SiCyMe₂-Cp)HfMe₂;(PrCp)(3-CH₂—SiCyMe₂-Cp)HfMe₂; (BuCp)(3-CH₂—SiCyMe₂-Cp)HfMe₂;(BzCp)(3-CH₂—SiCyMe₂-Cp)HfMe₂; (3-CH₂—SiCyMe₂-Cp)₂HfMe₂;(Me₂Cp)(3-CH₂—SiCyMe₂-Cp)HfMe₂; (Me₃Cp)(3-CH₂—SiCyMe₂-Cp)HfMe₂;(Me₄Cp)(3-CH₂—SiCyMe₂-Cp)HfMe₂; (Me₅Cp)(3-CH₂—SiCyMe₂-Cp)HfMe₂;(Et₂Cp)(3-CH₂—SiCyMe₂-Cp)HfMe₂; (Et₃Cp)(3-CH₂—SiCyMe₂-Cp)HfMe₂;(Et₄Cp)(3-CH₂—SiCyMe₂-Cp)HfMe₂; (Et₅Cp)(3-CH₂—SiCyMe₂-Cp)HfMe₂;(Pr₂Cp)(3-CH₂—SiCyMe₂-Cp)HfMe₂; (Pr₃Cp)(3-CH₂—SiCyMe₂-Cp)HfMe₂;(Pr₄Cp)(3-CH₂—SiCyMe₂-Cp)HfMe₂; (Pr₅Cp)(3-CH₂—SiCyMe₂-Cp)HfMe₂;(Bu₂Cp)(3-CH₂—SiCyMe₂-Cp)HfMe₂; (Bu₃Cp)(3-CH₂—SiCyMe₂-Cp)HfMe₂;(Bu₄Cp)(3-CH₂—SiCyMe₂-Cp)HfMe₂; (Bu₅Cp)(3-CH₂—SiCyMe₂-Cp)HfMe₂;(Bz₂Cp)(3-CH₂—SiCyMe₂-Cp)HfMe₂; (Bz₃Cp)(3-CH₂—SiCyMe₂-Cp)HfMe₂;(Bz₄Cp)(3-CH₂—SiCyMe₂-Cp)HfMe₂; (Bz₅Cp)(3-CH₂—SiCyMe₂-Cp)HfMe₂;(EtMe₄Cp)(3-CH₂—SiCyMe₂-Cp)HfMe₂; (PrMe₄Cp)(3-CH₂—SiCyMe₂-Cp)HfMe₂;(BuMe₄Cp)(3-CH₂—SiCyMe₂-Cp)HfMe₂; (BzMe₄Cp)(3-CH₂—SiCyMe₂-Cp)HfMe₂;(Me₄Cp-CH₂—SiMe₃)(3-CH₂—SiCyMe₂-Cp)HfMe₂;(Me₄Cp-CH₂—SiCyMe₂Ph)(3-CH₂—SiCyMe₂-Cp)HfMe₂;(Me₄Cp-CH₂—SiMePh₂)(3-CH₂—SiCyMe₂-Cp)HfMe₂;(Me₄Cp-CH₂—SiPh₃)(3-CH₂—SiCyMe₂-Cp)HfMe₂;(Me₄Cp-CH₂—SiMe₂Cy)(3-CH₂—SiCyMe₂-Cp)HfMe₂;(Me₄Cp-CH₂—SiMeCy₂)(3-CH₂—SiCyMe₂-Cp)HfMe₂;(Me₄Cp-CH₂—SiCy₃)(3-CH₂—SiCyMe₂-Cp)HfMe₂;(EtMe₃Cp)(3-CH₂—SiCyMe₂-Cp)HfMe₂; (PrMe₃Cp)(3-CH₂—SiCyMe₂-Cp)HfMe₂;(BuMe₃Cp)(3-CH₂—SiCyMe₂-Cp)HfMe₂; (BzMe₃Cp)(3-CH₂—SiCyMe₂-Cp)HfMe₂;(Me₃Cp-CH₂—SiMe₃)(3-CH₂—SiCyMe₂-Cp)HfMe₂;(Me₃Cp-CH₂—SiMe₂Ph)(3-CH₂—SiCyMe₂-Cp)HfMe₂;(Me₃Cp-CH₂—SiMePh₂)(3-CH₂—SiCyMe₂-Cp)HfMe₂;(Me₃Cp-CH₂—SiPh₃)(3-CH₂—SiCyMe₂-Cp)HfMe₂;(Me₃Cp-CH₂—SiMe₂Cy)(3-CH₂—SiCyMe₂-Cp)HfMe₂;(Me₃Cp-CH₂—SiMeCy₂)(3-CH₂—SiCyMe₂-Cp)HfMe₂;(Me₃Cp-CH₂—SiCy₃)(3-CH₂—SiCyMe₂-Cp)HfMe₂;(MeEtCp)(3-CH₂—SiCyMe₂-Cp)HfMe₂; (MePrCp)(3-CH₂—SiCyMe₂-Cp)HfMe₂;(MeBuCp)(3-CH₂—SiCyMe₂-Cp)HfMe₂; (BzMeCp)(3-CH₂—SiCyMe₂-Cp)HfMe₂;(EtPrCp)(3-CH₂—SiCyMe₂-Cp)HfMe₂; (EtBuCp)(3-CH₂—SiCyMe₂-Cp)HfMe₂;(BzEtCp)(3-CH₂—SiCyMe₂-Cp)HfMe₂; (PrBuCp)(3-CH₂—SiCyMe₂-Cp)HfMe₂;(BzPrCp)(3-CH₂—SiCyMe₂-Cp)HfMe₂; (BuBzCp)(3-CH₂—SiCyMe₂-Cp)HfMe₂;(Cp)(3—CH₂—SiCy₂Me-Cp)HfMe₂; (MeCp)(3-CH₂—SiCy₂Me-Cp)HfMe₂;(EtCp)(3-CH₂—SiCy₂Me-Cp)HfMe₂; (PrCp)(3-CH₂—SiCy₂Me-Cp)HfMe₂;(BuCp)(3-CH₂—SiCy₂Me-Cp)HfMe₂; (BzCp)(3-CH₂—SiCy₂Me-Cp)HfMe₂;(3-CH₂—SiCy₂Me-Cp)₂HfMe₂; (Me₂Cp)(3-CH₂—SiCy₂Me-Cp)HfMe₂;(Me₃Cp)(3-CH₂—SiCy₂Me-Cp)HfMe₂; (Me₄Cp)(3-CH₂—SiCy₂Me-Cp)HfMe₂;(Me₅Cp)(3-CH₂—SiCy₂Me-Cp)HfMe₂; (Et₂Cp)(3-CH₂—SiCy₂Me-Cp)HfMe₂;(Et₃Cp)(3-CH₂—SiCy₂Me-Cp)HfMe₂; (Et₄Cp)(3-CH₂—SiCy₂Me-Cp)HfMe₂;(Et₅Cp)(3-CH₂—SiCy₂Me-Cp)HfMe₂; (Pr₂Cp)(3-CH₂—SiCy₂Me-Cp)HfMe₂;(Pr₃Cp)(3-CH₂—SiCy₂Me-Cp)HfMe₂; (Pr₄Cp)(3-CH₂—SiCy₂Me-Cp)HfMe₂;(Pr₅Cp)(3-CH₂—SiCy₂Me-Cp)HfMe₂; (Bu₂Cp)(3-CH₂—SiCy₂Me-Cp)HfMe₂;(Bu₃Cp)(3-CH₂—SiCy₂Me-Cp)HfCl₂; (Bu₄Cp)(3-CH₂—SiCy₂Me-Cp)HfCl₂;(Bu₅Cp)(3-CH₂—SiCy₂Me-Cp)HfCl₂; (Bz₂Cp)(3-CH₂—SiCy₂Me-Cp)HfMe₂;(Bz₃Cp)(3-CH₂—SiCy₂Me-Cp)HfMe₂; (Bz₄Cp)(3-CH₂—SiCy₂Me-Cp)HfCl₂;(Bz₅Cp)(3-CH₂—SiCy₂Me-Cp)HfCl₂; (EtMe₄Cp)(3-CH₂—SiCy₂Me-Cp)HfCl₂;(PrMe₄Cp)(3-CH₂—SiCy₂Me-Cp)HfMe₂; (BuMe₄Cp)(3-CH₂—SiCy₂Me-Cp)HfMe₂;(BzMe₄Cp)(3-CH₂—SiCy₂Me-Cp)HfMe₂;(Me₄Cp-CH₂—SiMe₃)(3-CH₂—SiCy₂Me-Cp)HfMe₂;(Me₄Cp-CH₂—SiMe₂Ph)(3-CH₂—SiCy₂Me-Cp)HfMe₂;(Me₄Cp-CH₂—SiMePh₂)(3-CH₂—SiCy₂Me-Cp)HfMe₂;(Me₄Cp-CH₂—SiPh₃)(3-CH₂—SiCy₂Me-Cp)HfMe₂;(Me₄Cp-CH₂—SiMe₂Cy)(3-CH₂—SiCy₂Me-Cp)HfMe₂;(Me₄Cp-CH₂—SiMeCy₂)(3-CH₂—SiCy₂Me-Cp)HfMe₂;(Me₄Cp-CH₂—SiCy₃)(3-CH₂-Cy₂Me-Cp)HfMe₂;(EtMe₃Cp)(3-CH₂—SiCy₂Me-Cp)HfMe₂; (PrMe₃Cp)(3-CH₂—SiCy₂Me-Cp)HfMe₂;(BuMe₃Cp)(3-CH₂—SiCy₂Me-Cp)HfMe₂; (BzMe₃Cp)(3-CH₂—SiCy₂Me-Cp)HfMe₂;(Me₃Cp-CH₂—SiMe₃)(3-CH₂—SiCy₂Me-Cp)HfMe₂;(Me₃Cp-CH₂—SiMe₂Ph)(3-CH₂—SiCy₂Me-Cp)HfMe₂;(Me₃Cp-CH₂—SiMePh₂)(3-CH₂—SiCy₂Me-Cp)HfMe₂;(Me₃Cp-CH₂—SiPh₃)(3-CH₂—SiCy₂Me-Cp)HfMe₂;(Me₃Cp-CH₂—SiMe₂Cy)(3-CH₂—SiCy₂Me-Cp)HfMe₂;(Me₃Cp-CH₂—SiMeCy₂)(3-CH₂—SiCy₂Me-Cp)HfMe₂;(Me₃Cp-CH₂—SiCy₃)(3-CH₂—SiCy₂Me-Cp)HfMe₂;(MeEtCp)(3-CH₂—SiCy₂Me-Cp)HfMe₂; (MePrCp)(3-CH₂—SiCy₂Me-Cp)HfMe₂;(MeBuCp)(3-CH₂—SiCy₂Me-Cp)HfMe₂; (BzMeCp)(3-CH₂—SiCy₂Me-Cp)HfMe₂;(EtPrCp)(3-CH₂—SiCy₂Me-Cp)HfMe₂; (EtBuCp)(3-CH₂—SiCy₂Me-Cp)HfMe₂;(BzEtCp)(3-CH₂—SiCy₂Me-Cp)HfMe₂; (PrBuCp)(3-CH₂—SiCy₂Me-Cp)HfMe₂;(BzPrCp)(3-CH₂—SiCy₂Me-Cp)HfMe₂; (BuBzCp)(3-CH₂—SiCy₂Me-Cp)HfMe₂;(Cp)(3-CH₂—SiCy₃-Cp)HfMe₂; (MeCp)(3-CH₂—SiCy₃-Cp)HfMe₂;(EtCp)(3-CH₂—SiCy₃-Cp)HfMe₂; (PrCp)(3-CH₂—SiCy₃-Cp)HfMe₂;(BuCp)(3-CH₂—SiCy₃-Cp)HfMe₂ (BzCp)(3-CH₂—SiCy₃-Cp)HfMe₂;(3-CH₂—SiCy₃-Cp)₂HfMe₂; (Me₂Cp)(3-CH₂—SiCy₃-Cp)HfMe₂;(Me₃Cp)(3-CH₂—SiCy₃-Cp)HfMe₂; (Me₄Cp)(3-CH₂—SiCy₃-Cp)HfMe₂;(Me₅Cp)(3-CH₂—SiCy₃-Cp)HfMe₂; (Et₂Cp)(3-CH₂—SiCy₃-Cp)HfMe₂;(Et₃Cp)(3-CH₂—SiCy₃-Cp)HfMe₂; (Et₄Cp)(3-CH₂—SiCy₃-Cp)HfMe₂;(Et₅Cp)(3-CH₂—SiCy₃-Cp)HfMe₂; (Pr₂Cp)(3-CH₂—SiCy₃-Cp)HfMe₂;(Pr₃Cp)(3-CH₂—SiCy₃-Cp)HfMe₂; (Pr₄Cp)(3-CH₂—SiCy₃-Cp)HfMe₂;(Pr₅Cp)(3-CH₂—SiCy₃-Cp)HfMe₂; (Bu₂Cp)(3-CH₂—SiCy₃-Cp)HfMe₂;(Bu₃Cp)(3-CH₂—SiCy₃-Cp)HfMe₂; (Bu₄Cp)(3-CH₂—SiCy₃-Cp)HfMe₂;(Bu₅Cp)(3-CH₂—SiCy₃-Cp)HfMe₂; (Bz₂Cp)(3-CH₂—SiCy₃-Cp)HfMe₂;(Bz₃Cp)(3-CH₂—SiCy₃-Cp)HfMe₂; (Bz₄Cp)(3-CH₂—SiCy₃-Cp)HfMe₂;(Bz₅Cp)(3-CH₂—SiCy₃-Cp)HfMe₂; (EtMe₄CP)(3-CH₂—SiCy₃-Cp)HfMe₂;(PrMe₄Cp)(3-CH₂—SiCy₃-Cp)HfMe₂; (BuMe₄Cp)(3-CH₂—SiCy₃-Cp)HfMe₂;(BzMe₄Cp)(3-CH₂—SiCy₃-Cp)HfMe₂; (Me₄Cp-CH₂—SiMe₃)(3-CH₂—SiCy₃-Cp)HfMe₂;(Me₄Cp-CH₂—SiMe₂Ph)(3-CH₂—SiCy₃-Cp)HfMe₂;(Me₄Cp-CH₂—SiMePh₂)(3-CH₂—SiCy₃-Cp)HfMe₂;(Me₄Cp-CH₂—SiPh₃)(3-CH₂—SiCy₃-Cp)HfMe₂;(Me₄Cp-CH₂—SiMe₂Cy)(3-CH₂—SiCy₃-Cp)HfMe₂;(Me₄Cp-CH₂—SiMeCy₂)(3-CH₂—SiCy₃-Cp)HfMe₂;(Me₄Cp-CH₂—SiCy₃)(3-CH₂—SiCy₃-Cp)HfMe₂; (EtMe₃Cp)(3-CH₂—SiCy₃-Cp)HfMe₂;(PrMe₃Cp)(3-CH₂—SiCy₃-Cp)HfMe₂; (BuMe₃Cp)(3-CH₂—SiCy₃-Cp)HfMe₂;(BzMe₃Cp)(3-CH₂—SiCy₃-Cp)HfMe₂; (Me₃Cp-CH₂—SiMe₃)(3-CH₂—SiCy₃-Cp)HfMe₂;(Me₃Cp-CH₂—SiMe₂Ph)(3-CH₂—SiCy₃-Cp)HfMe₂;(Me₃Cp-CH₂—SiMePh₂)(3-CH₂—SiCy₃-Cp)HfMe₂;(Me₃Cp-CH₂—SiPh₃)(3-CH₂—SiCy₃-Cp)HfMe₂;(Me₃Cp-CH₂—SiMe₂Cy)(3-CH₂—SiCy₃-Cp)HfMe₂;(Me₃Cp-CH₂—SiMeCy₂)(3-CH₂—SiCy₃-Cp)HfMe₂;(Me₃Cp-CH₂—SiCy₃)(3-CH₂—SiCy₃-Cp)HfMe₂; (MeEtCp)(3-CH₂—SiCy₃-Cp)HfMe₂;(MePrCp)(3-CH₂—SiCy₃-Cp)HfMe₂; (MeBuCp)(3-CH₂—SiCy₃-Cp)HfMe₂;(BzMeCp)(3-CH₂—SiCy₃-Cp)HfMe₂; (EtBuCp)(3-CH₂—SiCy₃-Cp)HfMe₂;(BzEtCp)(3-CH₂—SiCy₃-Cp)HfMe₂; (PrBuCp)(3-CH₂—SiCy₃-Cp)HfMe₂;(BzPrCp)(3-CH₂—SiCy₃-Cp)HfMe₂; (BuBzCp)(3-CH₂—SiCy₃-Cp)HfMe₂;(2-Me,3-CH₂—SiMe₃-Ind)₂HfMe₂; (2-Et,3-CH₂—SiMe₃-Ind)₂HfMe₂;(2-Pr,3-CH₂—SiMe₃-Ind)₂HfMe₂; (2-Bu,3-CH₂—SiMe₃-Ind)₂HfMe₂;(2-Ph,3-CH₂—SiMe₃-Ind)₂HfMe₂; (2-Bz,3-CH₂—SiMe₃-Ind)₂HfMe₂;(2-Me,3-CH₂—SiMe₂Ph-Ind)₂HfMe₂; (2-Et,3-CH₂—SiMe₂Ph-Ind)₂HfMe₂;(2-Pr,3-CH₂—SiMe₂Ph-Ind)₂HfMe₂; (2-Bu,3-CH₂—SiMe₂Ph-Ind)₂HfMe₂;(2-Ph,3-CH₂—SiMe₂Ph-Ind)₂HfMe₂; (2-Bz,3-CH₂—SiMe₂Ph-Ind)₂HfMe₂;(2-Me,3-CH₂—SiMePh₂-Ind)₂HfMe₂; (2-Et,3-CH₂—SiMePh₂-Ind)₂HfMe₂;(2-Pr,3-CH₂—SiMePh₂-Ind)₂HfMe₂; (2-Bu,3-CH₂—SiMePh₂-Ind)₂HfMe₂;(2-Ph,3-CH₂—SiMePh₂-Ind)₂HfMe₂; (2-Bz,3-CH₂—SiMePh₂-Ind)₂HfMe₂;(2-Me,3-CH₂—SiPh₃-Ind)₂HfMe₂; (2-Et,3-CH₂—SiPh₃-Ind)₂HfMe₂;(2-Pr,3-CH₂—SiPh₃-Ind)₂HfMe₂; (2-Bu,3-CH₂—SiPh₃-Ind)₂HfMe₂;(2-Ph,3-CH₂—SiPh₃-Ind)₂HfMe₂; (2-Bz,3-CH₂—SiPh₃-Ind)₂HfMe₂;(2-Me,3-CH₂—SiCyMe₂-Ind)₂HfMe₂; (2-Et,3-CH₂—SiCyMe₂-Ind)₂HfMe₂;(2-Pr,3-CH₂—SiCyMe₂-Ind)₂HfMe₂; (2-Bu,3-CH₂—SiCyMe₂-Ind)₂HfMe₂;(2-Ph,3-CH₂—SiCyMe₂-Ind)₂HfMe₂; (2-Bz,3-CH₂—SiCyMe₂-Ind)₂HfMe₂;(2-Me,3-CH₂—SiCy₂Me-Ind)₂HfMe₂; (2-Et,3-CH₂—SiCy₂Me-Ind)₂HfMe₂;(2-Pr,3-CH₂—SiCy₂Me-Ind)₂HfMe₂; (2-Bu,3-CH₂—SiCy₂Me-Ind)₂HfMe₂;(2-Ph,3-CH₂—SiCy₂Me-Ind)₂HfMe₂; (2-Bz,3-CH₂—SiCy₂Me-Ind)₂HfMe₂;(2-Me,3-CH₂—SiCy₃-Ind)₂HfMe₂; (2-Et,3-CH₂—SiCy₃-Ind)₂HfMe₂;(2-Pr,3-CH₂—SiCy₃-Ind)₂HfMe₂; (2-Bu,3-CH₂—SiCy₃-Ind)₂HfMe₂;(2-Ph,3-CH₂—SiCy₃-Ind)₂HfMe₂; (2-Bz,3-CH₂—SiCy₃-Ind)₂HfMe₂;(2-Me,3-CH₂—SiMe₃-Ind)(3-CH₂—SiMe₃-Cp)HfMe₂;(2-Et,3-CH₂—SiMe₃-Ind)(3-CH₂—SiMe₃-Cp)HfMe₂;(2-Pr,3-CH₂—SiMe₃-Ind)(3-CH₂—SiMe₃-Cp)HfMe₂;(2-Bu,3-CH₂—SiMe₃-Ind)(3-CH₂—SiMe₃-Cp)HfMe₂;(2-Pn,3-CH₂—SiMe₃-Ind)(3-CH₂—SiMe₃-Cp)HfMe₂;(2-Hx,3-CH₂—SiMe₃-Ind)(3-CH₂—SiMe₃-Cp)HfMe₂;(2-Ph,3-CH₂—SiMe₃-Ind)(3-CH₂—SiMe₃-Cp)HfMe₂;(2-Me,3-CH₂—SiMe₂Ph-Ind)(3-CH₂—SiMe₃-Cp)HfMe₂;(2-Et,3-CH₂—SiMe₂Ph-Ind)(3-CH₂—SiMe₃-Cp)HfMe₂;(2-Pr,3-CH₂—SiMe₂Ph-Ind)(3-CH₂—SiMe₃-Cp)HfMe₂;(2-Bu,3-CH₂—SiMe₂Ph-Ind)(3-CH₂—SiMe₃-Cp)HfMe₂;(2-Pn,3-CH₂—SiMe₂Ph-Ind)(3-CH₂—SiMe₂Ph-Cp)HfMe₂;(2-Hx,3-CH₂—SiMe₂Ph-Ind)(3-CH₂—SiMe₃-Cp)HfMe₂;(2-Ph,3-CH₂—SiMe₂Ph-Ind)(3-CH₂—SiMe₃-Cp)HfMe₂;(2-Me,3-CH₂—SiMePh₂-Ind)(3-CH₂—SiMe₃-Cp)HfMe₂;(2-Et,3-CH₂—SiMePh₂-Ind)(3-CH₂—SiMe₃-Cp)HfMe₂;(2-Pr,3-CH₂—SiMePh₂-Ind)(3-CH₂—SiMe₃-Cp)HfMe₂;(2-Bu,3-CH₂—SiMePh₂-Ind)(3-CH₂—SiMe₃-Cp)HfMe₂;(2-Pn,3-CH₂—SiMePh₂-Ind)(3-CH₂—SiMe₂Ph-Cp)HfMe₂;(2-Hx,3-CH₂—SiMePh₂-Ind)(3-CH₂—SiMe₃-Cp)HfMe₂;(2-Ph,3-CH₂—SiMePh₂-Ind)(3-CH₂—SiMe₃-Cp)HfMe₂;(2-Me,3-CH₂—SiPh₃-Ind)(3-CH₂—SiMe₃-Cp)HfMe₂;(2-Et,3-CH₂—SiPh₃-Ind)(3-CH₂—SiMe₃-Cp)HfMe₂;(2-Pr,3-CH₂—SiPh₃-Ind)(3-CH₂—SiMe₃-Cp)HfMe₂;(2-Bu,3-CH₂—SiPh₃-Ind)(3-CH₂—SiMe₃-Cp)HfMe₂;(2-Pn,3-CH₂—SiPh₃-Ind)(3-CH₂—SiMe₂Ph-Cp)HfMe₂;(2-Hx,3-CH₂—SiPh₃-Ind)(3-CH₂—SiMe₃-Cp)HfMe₂;(2-Ph,3-CH₂—SiPh₃-Ind)(3-CH₂—SiMe₃-Cp)HfMe₂;(2-Me,3-CH₂—SiCyMe₂-Ind)(3-CH₂—SiMe₃-Cp)HfMe₂;(2-Et,3-CH₂—SiCyMe₂-Ind)(3-CH₂—SiMe₃-Cp)HfMe₂;(2-Pr,3-CH₂—SiCyMe₂-Ind)(3-CH₂—SiMe₃-Cp)HfMe₂;(2-Bu,3-CH₂—SiCyMe₂-Ind)(3-CH₂—SiMe₃-Cp)HfMe₂;(2-Pn,3-CH₂—SiCyMe₂-Ind)(3-CH₂—SiMe₂Ph-Cp)HfMe₂;(2-Hx,3-CH₂—SiCyMe₂-Ind)(3-CH₂—SiMe₃-Cp)HfMe₂;(2-Ph,3-CH₂—SiCyMe₂-Ind)(3-CH₂—SiMe₃-Cp)HfMe₂, and the alkyl or halideversions thereof where the Me₂ is replaced with Bz₂, Et₂, Ph₂, Cl₂, Br₂,or I₂.
 17. A process for polymerization of olefin monomers comprisingcontacting one or more olefin monomers with the supported catalystsystem of claim
 1. 18. The process of claim 17, wherein polymerizationof the olefin monomers forms linear low density polyethylene.
 19. Aprocess for the production of an ethylene alpha-olefin copolymercomprising: polymerizing ethylene and at least one C₃-C₂₀ alpha-olefinby contacting the ethylene and the at least one C₃-C₂₀ alpha-olefin withthe supported catalyst of claim 1 in at least one gas phase reactor at areactor pressure of from 0.7 to 70 bar and a reactor temperature of from20° C. to 150° C. to form an ethylene alpha-olefin copolymer.
 20. Aprocess for the production of an ethylene alpha-olefin copolymercomprising: polymerizing ethylene and at least one C₃-C₂₀ alpha-olefinby contacting the ethylene and the at least one C₃-C₂₀ alpha-olefin withthe supported catalyst of claim 1 in at least one slurry phase reactorat a reactor pressure of from 0.7 to 70 bar and a reactor temperature offrom 60° C. to 130° C. to form an ethylene alpha-olefin copolymer. 21.An ethylene alpha-olefin copolymer obtained by contacting ethylene, atleast one C₃-C₂₀ alpha-olefin, and the supported catalyst of claim 1 inat least one gas-phase reactor, the copolymer having a density of 0.890g/cc or more, a melt index from 0.1 to 80 g/10 min, and an Mw/Mn valuefrom 1 to
 15. 22. The ethylene alpha-olefin copolymer of claim 21,wherein the copolymer has a density from 0.900 to 0.940 g/cc.
 23. Theethylene alpha-olefin copolymer of claim 21, wherein the copolymer hasan Mz/Mw between 2 and
 3. 24. The ethylene alpha-olefin copolymer ofclaim 21, wherein the copolymer has an Mw value of 50,000 to 250,000g/mol; an Mw/Mn value of 2.5 to 12.5; a density of from 0.900 to 0.940g/cc; and an Mz/Mw between 2 and
 3. 25. An ethylene alpha-olefincopolymer obtained by contacting ethylene, at least one C₃-C₂₀alpha-olefin, and the supported catalyst of claim 1 in at least oneslurry phase reactor, the copolymer having a density of 0.890 g/cc ormore, a melt flow index from 0.1 g/10 min to 80 g/10 min, and a Mw/Mnfrom 2.5 to 12.5.
 26. An ethylene alpha-olefin copolymer obtained bycontacting ethylene, at least one C₃-C₂₀ alpha-olefin, and the supportedcatalyst of claim 1 in at least one gas phase reactor, the copolymerhaving a density of 0.890 g/cc or more, a melt flow index from 0.1 g/10min to 80 g/10 min, and a Mw/Mn from 2.5 to 12.5, and a RCI,m between100 and 200 and a CDR-2 m between 1.5 and 2.5.
 27. An ethylenealpha-olefin copolymer obtained by contacting ethylene, at least oneC₃-C₂₀ alpha-olefin, and the supported catalyst of claim 1 in at leastone gas phase reactor, the copolymer having a density of 0.890 g/cc ormore, a melt flow index from 0.1 g/10 min to 80 g/10 min, a Mw/Mn offrom 2.0 to 5.0, a Mz/Mw between 2 and 3, a RCI,m between 30 and 100,and a CDR-2 m between 1 and 2.